Principles of Chemistry

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Title
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PRINCIPLES OF Chemistry
JOEL
H.
HILDEBRAND,
PH.D.,
SCO.
PROFESSOR OF CHEMISTRY IN THE UNIVERSITY OF CALIFORNIA
AND RICHARD
E.
POWELL, PH.D.
IN
ASSOCIATE PROFESSOR OF CHEMISTRY CALIFORNIA
THE UNIVERSITY OF
SIXTH EDITION
NEW YORK rH
MA
MTL f-XN
O"M
P.
A N Y
Sixth Edition Copyright, 1952, by

All rights reserved
The Macmillan Company
no part of
this
any form without permission in except by a reviewer who wishes
book may be reproduced in writing from the publisher,
to quote brief passages in connection with a review written for inclusion in magazine ot
newspaper.
PRINTED IN THE UNITED STATES OF AMERICA

Fourth Printing, 1956
RENEWAL COPYRIGHT,
1945,
BY JOEL
H.
HILDEBRAND
PREVIOUS EDITIONS COPYRIGHT, 1918, 1926, 1932, 1940, AND 1947, BY
THE MACMILLAN COMPANY
PREFACE TO THE SIXTH EDITION

This revision has been made
in presentation evolving
in order to
maintain the prac-
improvements from the experience, year after year, of an exceptionally competent group of instructors, and, second, to keep the book abreast of such advances in chemistry as even freshmen can appreciate, and thus to do some justice to
the exciting, dynamic character of this great field of knowledge. We have not felt it necessary to make a major revision at this
tice of thirty-four years, first, of incorporating
time because the preceding edition was extensively rewritten; the main alterations are to be found in the chapters dealing with the structure of matter, the properties of atoms, chemical
considbinding, chemical kinetics, equilibrium, and oxidation. erable number of minor alterations have been made throughout the text in the interest of clarity and style.
not intended either to replace or to confine the teacher. He is free to take up topics in any reasonable order and to embellish them with all the wealth of illustration at his
is
The book
command.
does not present one person's notions of how general chemistry should be taught, but is rather the fruit of
It
cooperative effort by members of a large department who have believed that good research and good teaching are equal obligations.
JOEL H. HILDEBRAND RICHARD E. POWELL

Berkeley, California
PREFACE TO THE FIFTH COITION

This fifth edition, like its predecessors, has been written in a continuing faith in perfection as a goal but not as an achievement. This has necessitated repeated revisions; indeed, the
present volume would hardly recognize its progenitor of thirty years ago. The changes have been, in part, of a pedagogical kind. In this I have profited, as heretofore, from criti-
own staff, whose members, senior as well as have always willingly cooperated by taking quiz junior, sections, but this time, particularly from suggestions gathered by the publisher at my request from users of the book in other institutions. I wish here to express my gratitude for the pains several of these teachers have taken. I have made
cisms by our
most of the changes indicated by their friendly criticisms. But changes and additions in subject matter have also been called for by the constant growth of the science itself.
dips facts from a stagnant reservoir is hardly teaching science; rather, he owes it to his students to give them the impression of an endowing stream. Chemistry
is
One who merely
in such a fluid state that it lends itself readily to this
eries in
purpose. Indeed, the young chemist needs the recent discovatomic structure to illumimite physical and chemical
properties. Conventional instruction in physics postpones this for a couple of years, but we can set this exciting story before
him in the freshman year. We can escape the restrictions what I have called, on page 80, the "chronological" order
presentation, according to which must be learned first.
all
of
of
the oldest knowledge
and digestive powers of different students vary enormously, far beyond the range between the traditional 60 and 100 per cent. Teachers should both teach and grade with the Gaussian curve in mind, and
Of
course, the intellectual appetites
VI
PREFACE TO THE FIFTH EDITION
vii
try to stimulate their best students to achieve not merely a fraction above but several times the average.
seems worthwhile here to repeat an explanation of our practice in the University of California to allow for this wide spread. I have heard our plan of instruction questioned as too difficult for average students, but I believe we treat them with due consideration. Although we deliberately set before all students a far richer fare than most of them can assimilate, we do not expect everyone to tackle every item. One device is to distinguish the entrees from the hors d'oeuvres, as in this volume by the use of different kinds of type, and asterisks for the difficult exercises at the end of chapters. One of our
It
weekly quizzes will contain decreasing credit, as in the following sample of a quiz given near the close of the first term
:
Divide the following substances into three groups according as dilute aqueous solutions made from them are acid, alkaline, or
1.
neutral
(1)
KC1
(2)
4
(6)
KHS0
(7)
NH NO NH Ac
4
(3)
(8)
BaCl 2
A1 2 (SO 4 ) 3
(4)
(9)
SrO
(5)
3
BaAc 2
NH
(10)
Na CO 3
2
Credit 30
2.
State what you can about the concentration of
H+
in
each of
the following:
(1) 0.05
M-H 2 SO
(5)
M-KAc
M-BaCl 2
lf-NH Ac
4
(9)
0.05
M-KHSO 4
M-HAc.
Credit 20
(2) 0.2 7V-H 2 SO 4 (3)

1
(6) 0.1
^T-NH 4 C1
(7)
3
M-NH.3
and 0.02M-HC1 in the same solution.

(10) 0.01
(4) 0.5
M-K CO
2
(8) 0.01
3.
If
a soluble base,
solution,
what
0.4 per cent ionized in 0.2 molal are the concentrations of M+, OH~, and
is
MOH,
MOH?
Credit 10
4.
What
is
the ionization constant of the
MOH
in the
above
case?
Credit 5
Set up the four equations from which you could calculate the 3 solution. concentration of OH" in 0.1 molal Credit 5
5.
MNO
viii
Such an arrangement permits the ordinary student to get enough points for a "C" grade from two easier questions to prevent discouragement, but the student who earns an "A" grade must answer the difficult third, fourth, and fifth
questions.
chapters or paragraphs have been added on systems of acids and bases, polymers, trans-uranium elements, structure of inorganic compounds, silicones, and carbonic acid and
its ions.
New
The
last of these offers excellent drill, in
tive
and quantitative,
both qualitathe principles of equilibrium as
applied to substances of great significance in biology, geology, industry, and the home.
Acid-Base Sysa careful explanation of the "Bronsted Theory,'* tems," along with the others. I fully appreciate the usefulness of this system for the purposes for which it is appropriate, but I have not used it throughout the rest of the book for two
I
have given,
in
Chapter
XXII
entitled
"
first, I regard it as better pedagogy to begin with the ordinary water system, extending to the proton-donoracceptor system later for the special purposes of organic
reasons:
chemistry; and, second, because the other systems are equally "right" and so much more useful for certain purposes that the Bronsted viewpoint should not be allowed to usurp the field. I have stated the criteria in paragraph 18 of the chapter. A teacher in another institution has stated his experience
regarding the pedagogic difficulties as follows: "At our institution I have been required to present the Bronsted definitions as the definitions of acids and bases. To avoid confusion and doubts, the students are not supposed to be made aware
of the existence of other points of view.
great difficulty with the presentation as simple as possible, then conclude that the students haven't grasped it, so we go over it again, and again.
The students have Bronsted concept. We make the
We
spend an inordinate amount of time on it and then recognize that the students have digested very little of it, so we ask practically nothing about it in the examinations. For the sake of simplicity we practically ignore the Bronsted con-
ix
cepts in the remainder of the course. All in all, the result is a mess. I believe the majority of our freshman staff agrees with
me
in this conclusion,
and
believe the Bronsted theory

I
is
ignored completely decidedly not in favor of 'going Bronsted' in the freshman

courses.
"
in the analytical courses that follow.
am
Many new exercises have been added, and the answers have been transferred to an appendix to combat the temptation to estimate them instead of working them out by analysis.
I wish, finally, to express my gratitude to my colleague, Professor Kenneth S. Pitzer, and to my former colleague,
Professor
for specific contributions, to Dr.
James Arthur Campbell, now of Oberlin College, Ralph R. Hultgren, Pro3-6 in
fessor of Physical Metallurgy, for the prints for Figs.
my colleague, Professor Glenn T. Seaborg, Chapter I, of the material on the trans-uranium elements. for criticism
and to
JOKL H. HILDEBRAND
p
Berkeley
California
TABLE OF CONTENTS
I.
II.
KINDS OF MATTER WEIGHT RELATIONS IN CHEMICAL REACTIONS
III.
IV.
V.
VI.
VII.
VIII.
ATOMS AND MOLECULES THE KINETIC THEORY MOLECULAR WEIGHTS THE RELATION OF CHEMICAL AND PHYSICAL PROPERTIES TO ATOMIC STRUCTURE ... CONCENTRATION, ACIDIMETRY AND ALKALIMETRY THERMOCHEMISTRY
ELECTROLYTIC DISSOCIATION COMBINING PROPORTIONS CHEMICAL NOMENCLATURE THE SPEED OF CHEMICAL REACTIONS ... CHEMICAL EQUILIBRIUM. THE EFFECT OF CONCENTRATION TYPES OF EQUILIBRIA THE EFFECT OF PRESSURE AND TEMPERATURE UPON EQUILIBRIUM OXIDATION AND REDUCTION THE CONSTITUTION OF THE ATOM THE PERIODIC SYSTEM OF ELEMENTS ORGANIC CHEMISTRY DISPERSED SYSTEMS SOLUBILTY CARBONIC ACID AND ITS IONS ACID-BASE SYSTEMS STRUCTURES OF INORGANIC COMPOUNDS
. .
19
36
63
80
IO7 Il8 127
IX.
146
154 1 62
X.
XI.
XII.
172 193
XIII.
XIV.
232
XV.
XVI.
XVII.
XVIII.
^
246 279
XIX.
306 328 353

37?
XX.
XXI.
XXII.
386
399 413
xii
TABLE OF CONTENTS
I.
APPENDIX
FINAL EXAMINATION QUESTIONS
...
423
433
APPENDIX II. ANSWERS TO EXERCISES AT THE ENDS OF CHAPTERS

INDEX
437
CHAPTER
KINDS OF MATTER
Chemistry? The answer to this question, apbook or a course, might be in various ways. One would be to give a definition, attempted which students could commit to memory and recite whenever called upon; a process which, from time immemorial, has been a prominent feature of education. The weakness of this method lies in the fact that definitions are often mere
1.
What
Is
propriate at the beginning of a
words, giving only the illusion of understanding to those who repeat them. Big subjects cannot be expressed at all adequately in sentence definitions. Dictionaries must give definitions but the full meaning of, say "friendship/' requires
an essay, a book, or still better, long experience. The scope of chemistry, similarly, is but dimly conveyed by its definition
in the dictionary, and will be found by the inquiring student to be a continually enlarging and interesting subject. This chapter is intended to give only a partial exposition of the
scope of chemistry, to be expanded throughout the entire book and through firsthand contact in the laboratory. 2. This distrust of definitions may seem inconsistent with
calls for definitions that will be found in the exercises at the end of this and other chapters. The intention is not that the student should ransack his memory, but that he should endeavor, solely as an exercise, to put into clear concise English whatever degree of comprehension he may have Attained at the time. A clear concept can be put into words, but words are no guarantee that the concept is clear. Not all definitions are subject to the above difficulties.
units of length, volume, mass, time, and so on, are clearly defined, also properties such as density, specific heat, solubility, viscosity. It may be interesting, as we proceed, to
1
The
PRINCIPLES OF CHEMISTRY
Ch.
notice which terms are capable of rigid definitions and which are not. (Cf. Exercise 5 at the end of this chapter.) 3. Many teachers of chemistry have felt it necessary to
Such a distinction and undesirable, as is clearly shown is arbitrary, unnecessary, by the existence of a large common domain known as "physical chemistry/' There is published a Journal of Physical Chemistry and also a Journal of Chemical Physics. This does not imply that there is no difference between chemistry and physics, but only that the differences lie in emphasis or in point of view, or sometimes only in the label on the laboratory in which a piece of work has been done. Our language is full of similar contrasting terms: bright and dull, rich and poor, blonde and brunette, fast and slow. These are useful enough, but the lines between them are either hazy or arbitrary. To a student no better illustration of this is needed than the grading practices of at least some of his professors.
define chemistry as distinct from physics.
We may now return to our question, What is chemistry? with the understanding that it is to be answered by no single sentence, propounded on the authority of the author to be memorized and recited by the student, but rather by a sort of aerial reconnaissance to get at least a preliminary and partial view of what is contained in the domain of chemistry.
and physics, like the oceans, are no recognizable line of demarkation, or if the separated by
If
we
find that chemistry
line is purely arbitrary, like the Arctic Circle, expect to have to jump across it.
4.
we
shall not
of
Substances and Their Properties. Chemistry is, first all, concerned with substances, materials, or kinds of matter, such as wood, glass, iron, copper, clay, sugar, each recognizable by its inherent properties, such as color, taste,
odor, hardness, density, etc. The names of substances must not be confused with the names of objects or articles, such as log, bottle, coin, brick, which are made of certain substances. Again, the forms which may be artificially imposed upon matter are not properties. It is a natural property of glass to become plastic at elevated temperatures, which
KINDS OF MATTER
permits it to be shaped into a variety of useful articles, but the glass does not assume these shapes of itself, hence they
are not properties of glass. The only forms which are inherent, serving to identify materials, are the crystal forms which most of them are able to assume on separating as solids
from the liquid or gaseous
states.
use the more obvious qualitative properties of matter to identify the substances encountered in daily life: the color of copper, the luster of silver, the taste of sugar or salt, the
Properties (Partial List)
We
Absorption spectrum
+ Boiling
Color
point ^Coefficient of expansion
Heat oi ^combustion
dissociation
expansion
"^formation fusion
ionization reaction
"^vaporization
Ignition temperature Index of refraction
Compressibility
Conductivity for heat Conductivity for electricity

Critical pressure Critical temperature Critical
volume
Crystal form
+ Density
Dielectric constant
Luster
Elastic limit
Elasticity
Magnetic susceptibility +Melting point
Odor
Reflectivity
Solubility Surface tension
Emission spectrum Emissivity
Entropy
Fluidity
Tensile strength
Free energy
+ Vapor pressure
Viscosity
Hardness
hardness and transparency of glass, the melting of ice, the low density of aluminum. We readily distinguish solids,
liquids, and gases. There are, however, many properties which are not evident to our unaided senses but which can be measured, often with great accuracy, by the aid of suitable
instruments, such as electrical conductivity, refractive index, coefficient of expansion. Since chemists, physicists, and en1 Cf. Latimer and Hildebrand, Reference Book of Inorganic Chemistry, York, The Macmillan Company, 1951, Appendix V.
New
PRINCIPLESOFCHEMISTRY
Ch.
gineers have several hundred thousand different substances to identify and utilize, it is important to be able to measure
all
table
the properties with the requisite degree of accuracy. The on p. 3 is an incomplete list of properties. The student would do well to be able to define or explain or describe a method for measuring as many of these properties as possible,
particularly those
Glossary in Reference
marked by +. Use may be made of the Book of Inorganic Chemistry, p. 513,
by Latimer and Hildebrand. 5. Chemical Reactions. Substances may change into other substances by processes called chemical reactions. Among the countless examples may be mentioned the rusting of iron, the
burning of fuel, the fermentation of sugar, the explosion of gunpowder, the digestion of food, and the solution of silver in nitric acid. The ability of a substance to undergo a given chemical change is one of its chemical properties, aiding in its identification. Thus starch and talc may be distinguished by the fact that the former will burn in air but the latter will not. Silver will dissolve in nitric acid, tin reacts with the same acid to give a white insoluble powder, platinum will not react with it at all.
6.
The
What
quantities involved are often important to know. weights of iron ore and coke are necessary to produce
a ton of iron?
What
proportions of baking soda and cream
of tartar should be used for a
baking powder? It is part of chemistry to be able to answer such questions. 7. Or again, we may be chiefly interested not in the nature of the substances involved but in the amount of energy liberated in the form of light, heat, or mechanical power.
purchase flashlight cells for the electrical energy liberated by the chemical reaction that goes on in the cells while in use. In the manufacture of substances by electrochemical processes, such as chlorine, caustic soda, aluminum, and magnesium, the cost of the electrical energy that must be supplied is as important as the cost of the raw materials that must be used. 8. We may summarize our view of the field of chemistry up to this point by saying that chemistry is concerned with
We
10
KINDSOFMATTER
substances and their properties; with the techniques for separating one substance from another; with the changes or reactions whereby other substances are formed; with the
conditions necessary for bringing about or preventing these reactions; and with the relative amounts of matter and energy
involved.
9.
less
Various motives may lead one to study chemistry. More or knowledge of the subject is essential for agriculture, engineering
its
branches, medicine, the biological sciences, and most manufacturing industries. Again, all persons whose minds are
in
all
environment
concerning their environment. This and chemical as well as social and economic. physical Again, chemistry if studied properly as a science gives unsurpassed training in the scientific method, one of the major intellectual achievements of mankind. Chemistry, first of all, has progressed much farther than certain other sciences beyond the era of mere description and classification; second, it shares with physics and astronomy a good deal of mathematical rigor, while presenting at the same time phenomena too complicated, as yet, for mathematical treatment and which must be dealt with by more qualitative
active
feel
lively
is
curiosity
methods such as are

method, tion but
like
it
largely characteristic of biology. The scientific itself, is not subject to brief, precise definiincludes the search for pertinent facts, the planning and
chemistry
performing of experiments carefully designed to reveal new facts and relationships; the use of the imagination to form hypotheses, along with scrupulous care and honesty in subjecting them to the tests both of facts and logic. Such training has both moral and intellectual value and although it is difficult for man to transfer the lessons he learns from one realm to another, nevertheless the prob-
lems presented in other fields, particularly the social, political, and economic, are so pressing and complicated that both the desire and ability to attack them scientifically is of the utmost importance. It is the hope of the author that the students of this book will find not only that they have learned about substances and their transformations but will find themselves more inclined as well as able to treat scientifically, all problems, whether chemistry or not,
which are appropriate

10.
for scientific treatment.
Mixtures. As
guish substances,
we attempt to apply our tests to distinwe notice that for some materials the an-
Ch.
swers vary from sample to sample. What are the properties of granite? Of solder? Of salt water? Each of these is in fact a mixture of two or more substances. The term "mixture" is applied loosely to the result of any mixing process in housewife may obvious chemical reaction occurs.
which no mix flour,
baking powder, sugar,
salt,
husband mixes a
1
cocktail.
and lard for biscuit batter while her Both the batter and the cocktail are
'mixtures.
"
properties of a mixture depend upon its composition, the relative amounts of its various constituents. Therei.e., fore, when we report the properties of a mixture, we must also specify its composition. We can state, as precisely as we wish,
The
the properties of a solder which
is
50%
tin
and
50%
lead, or of
2%
11.
salt solution.
Heterogeneous Mixtures. Even to the naked eye, granite is composed of several kinds of minerals. At each boundary from one small region to another, its properties change
abruptly. All of the regions of the
called heterogeneous. Granite
same kind together constitute

is
a phase, and a mixture containing more than one phase

is
a heterogeneous mixture of
three phases: quartz, mica, and feldspar.

ice
A mixtiire of chopped
and the
salt
and
liquid
water
is
ture used in
making
ice
heterogeneous. So is the freezing mixcream all of the pieces of ice together

:
constitute one phase, the crystals of salt another, solution the third.
rock, a slurry of sand
Heterogeneity can often be detected by the unaided eye: a supended in water, a layer of kerosene floating in water, a foam (gas bubbles mixed with a liquid). If one of the phases is finely divided, the mixture may only
appear cloudy to the eye, but the individual particles can readily be seen under a microscope; examples include paint (solid dispersed in liquid), milk (fat droplets dispersed in an
aqueous medium), fog

(solid particles in gas).
(liquid
Some
droplets in gas), and smoke alloys appear uniform to the eye,
but careful etching with acid and examination using a microscope with reflected light reveals that they are heterogeneous. Solder, for example, is made up of crystals of tin and crystals
11
KINDS OF MATTER
Grey cast iron contains graphite crystals, as shown and is obviously heterogeneous, as is annealed steel,
in-
of lead.
in Fig. 2,
Fig. 3,
which consists of an
timate mixture of pure iron with an iron carbide.
Another technique
for de-
tecting heterogeneity in solids makes use of X-ray diffraction.
When a beam of
in the
X-rays
is
shot
into a solid, the X-rays emerge
same
direction,
and
of
in
addition in a
directions.
number
new
these
1
cipal
The angles between new beams and the prinbeam are absolutely chart
i
acteristic of the kind of crystal
they are the "fingerprints" of the crystal. Suppose we melt together some sodium chloride and some potassium chloride, and cool the melt until it solidifies.
r tg- 1. Photograph iHKen tnrouen rriotocrapn taken through Fig. * 8 p a microscope of a fa mihar he terogeneus system, oil emulsified in water by the aid of soap
*
Is the resulting solid.
heterogeneous or not?
We
find that
Fig. 2.
Grey
cast iron.
Fig. 3.
Annealed
steel.
the X-ray diffraction pattern of this solid is a superposition of the patterns of sodium chloride and of potassium chloride so we know that the solid contains the two kinds of crystals
and
is
heterogeneous.
8
12.
The Separation
of
Chi
If
Heterogeneous Mixtures.
constituents,
we wish
the rock
to separate granite into
its
we may crush
and then pick out fragments of the individual minerals. In this way we can obtain enough samples to identify the constituents. Let us devise a technique which will permit their separation on
be composed of mica whose density is 2.80, and feldspar whose density is 2.56. If we powder the granite and throw it into a liquid whose density is 2.60, the feldspar will float while the quartz and mica will sink. If we then change to a liquid whose density is 2.70, the quartz will float and the mica will sink. Such "float-or-sink" separations, which take ada larger
scale.
Suppose we
find the granite to
quartz whose density
is 2.65,
vantage of differences in density, are often useful. A similar technique is used in the "panning" of gold; the solid gold (density 19) remains in the pan while the agitated water carries away the sand (density 2.65). Density methods are also used to separate gases from liquids, two liquids from each other, and solids from liquids. On account of the very low density of gases, a gas will always rise to the top of a liquid in which it is not soluble, when the gas can be pumped away or the liquid drained off. For this reason, gases are often collected and manipulated above a liquid such as water or mercury. Two liquids which do not mix can easily be separated by use of a "separatory funnel," which is provided with a stopcock at the bottom for draining off the denser liquid layer. To separate a solid from a liquid, the solid may be allowed to settle to the bottom, and the supernatant liquid poured off ("decanted"). Instead of relying on the force of gravity to separate two phases of different density, we may use centrifugal force.
One example
of this
is
the centrifuge which
the "cream separator," and another i$ is used in the analytical laboratory to
separate precipitates from solutions.
suspended
solid is
commonly removed from a
liquid
by
filtration.
A fog or a smoke may be
removed from a gas by the
same means.
Let us dissolve a teaspoonful of sugar in a glass of water. The resulting mixture is not visibly heterogene13. Solutions.
13
KINDS OF MATTER
ous,
even under a microscope; the sugar does not settle out, nor can it be filtered out. The sugar-water is in fact a single phase (it is homogeneous). A single phase may consist of one pure substance (such as pure sugar, pure iron, pure liquid
water), or
it
may
consist of
it is
two or more substances
(like sugar-
Although the most familiar solutions are liquid solutions, the term "solution" is not restricted to liquids. All gases are completely miscible with one another, forming but one phase, so that every mixture of gases is a gaseous solution. The alloy of silver with gold, no matter what the relative amounts of the two metals, contains but one kind of crystal, so is said to be a solid
water) in which case
called a solution.
solution.
Hardened
a
solid
steel
is
likewise
solution, for
though it contains carbon it shows but one kind of crystal under the microscope, as
shown
in Fig. 4.
Fig. 4.
experiments will tell us whether a particular sample

is
What
Hardened
steel;
a solid
solution.
tion?
a pure substance or a soluThe most convenient criteria are the melting point, the
boiling point,
and the
solubility in
some
suitable solvent.
For
a pure substance, these are sharply defined properties. For a

solution, these properties depend upon the composition, which varies during the melting (or boiling, or dissolving) process. Solutions therefore exhibit a range of melting point, or boil-
ing point, or solubility. few actual examples:

(a)
first
We
can
illustrate the principle
with a
Melting point. The freezing point of liquid water (i.e., the temperature at which solid can appear as the liquid is C. The melting point of ice (i.e., the temperature cooled) is at which liquid first appears as the solid is warmed) is likewise
C.
As a matter of
fact, the freezing
point
is
identical with the
10
Ch.
melting point for any pure substance. For pure ethyl alcohol, the freezing point (and the melting point) is 110.5C. we have a liquid solution of 20% ethyl alcohol Suppose, now,
and
cool the liquid, solid can first appear at 10 C. (the freezing point). If we freeze the entire sample, and then warm it until the first liquid appears, we observe this
80%
water.
As we
to occur at
between
10 and
118 C. (the melting point). At any temperature 1 18, the sample will be a mixture of solid
is
with liquid, and the mixture
said to
have a melting range
of
-10
(b)
to
-118C.
The boiling point of pure nitrogen (i.e., the at which the gas pressure becomes one atmosphere, temperature 195.8 C., and its condensation as the liquid is warmed) is
Boiling point.
point (i.e., the temperature at which liquid can first appear, as the gas is cooled at a pressure of one eitmosphere) is likewise
195.8
C.
The
boiling point coincides with the condensation
point for
is
any pure substance. For pure oxygen, the boiling 183.0 C. and the condensation point is the same. point is a gaseous solution, of approximately 20% oxygen and Air
80%
air is
nitrogen
of this fact
by volume. Suppose, however, we were ignorant and wished to determine by experiinent whether
air until
a pure substance or a gaseous solution. We could cool the we reached its condensation temperature, which we
191. 7 C. Then we could liquefy the air would note to be completely, and warm it until its boiling point was reached, 194.2 C. We would then be able to which would occur at 194.2 to that air has a boiling range of 191.7, and say
accordingly
(c)
is
not a pure substance.
potassium sulfate in water at 25 C. is 12.1 grams per hundred grams of water, and this figure is not exceeded, no matter how much extra solid
Solubility.
The
solubility of pure
potassium sulfate is added. The solubility of pure ammonium sulfate in water at 25 C. is 77.0 grams per hundn d grams of
water, and this figure likewise is unaffected by the presence of additional solid ammonium sulfate. Suppose we melt together
equal weights of potassium sulfate and ammonium sulfate, and allow the melt to solidify; the resulting solid shows only one
15
KINDS OF MATTER
11
kind of crystal, so it is a solid solution. If we were handed a sample of such crystals, and asked to ascertain whether it was a pure substance, we might proceed as follows: To one hundred grams of water, we add crystals until some solid remains undissolved. This requires 23.8 grams of crystals. We continue to add solid until a large excess of it is present, then withdraw a sample of the liquid and analyze it. It is found to contain 66.7 grams of dissolved solid per hundred grams of water. Since the solid shows a range of solubility, depending on the amount of excess solid present, it cannot be a pure substance. 14. The Fractionation of Solutions. If a solution is partially
frozen, or partially evaporated, or partially dissolved, it is thereby separated into two phases whose compositions are, in
For example, if a solution of sugar and water is heated carefully, all the water will go into the gas phase and pure sugar will be left behind. If the solution of alcohol in water mentioned earlier is cooled to 115 C., it will separate into a solid phase which is pure ice and a liquid phase which is 93% alcohol. If air is cooled until half of it has been liquefied, the gas phase will be 10% oxygen and 90% nitrogen, while the liquid phase will be 30% oxygen and 70% nitrogen. If the potassium sulfate-ammonium sulfate solid is allowed to come to equilibrium with just enough water to dissolve half of it, the remaining solid will be 80% potassium sulfate and 20% ammonium sulfate, while the dissolved solid will be 80% ammonium sulfate and 20% potassium sulfate. After the two phases of different composition have been separated by mechanical means, each of them can be subjected to another partial phase change. By a systematic repetition
general, different.
of these fractional phase changes, any solution can eventually be separated into its components with any desired degree of purity.
The Elements. At least one-half million pure substances and new ones are constantly being prepared. However, they in turn are combinations of a much smaller number of simpler substances, called elements. Ninety-eight elements are known at the present time. Table 1 contains a list
15.
are known,
12
Ch.
of the chemical elements.

stances;
Many
of
them
are well
known
sub-
many
are rare, occurring in but small quantities.
In order to demonstrate that a pure substance is composed of two or more elements (or, as chemists would say, is a compound), we may seek to decompose the substance in question
" into its elements, a process called analysis, meaning taking apart"; or we may cause the elements to combine to form the
substance, a process called synthesis, meaning

gether."
'
'putting to-
For example, if we pass an electric current through water, using platinum or gold electrodes to introduce the current into the water, we find that the water is used up, and that the pure
gaseous element hydrogen appears at one electrode, the pure gaseous element oxygen at the other. From this analysis we
conclude that water
is
a compound of hydrogen and oxygen.
Alternatively, we can mix hydrogen with oxygen and ignite the mixture with a spark. The two gases will combine explosively, and when we recover the product of the reaction we
find
it
to be pure water.
is
that water
From this synthesis, also, we conclude a compound of hydrogen and oxygen.

grams of lead reacts with oxygen, the product
16. If 100
of the reaction weighs 108 grams; if the lead reacts instead with sulfur, the product weighs 116 grams; with chlorine the
product weighs 134 grams, with bromine 177 grams. Every compound of lead weighs more than the elemental lead from which it was prepared the increase in weight is, of course, due to the other element entering into the combination. It is the change in weight which enables us to decide definitely whether the product of a reaction is simpler or more complex. If, for example, we ignite a ribbon of magnesium in
;
of the reaction
it will burn brilliantly. The product a white powder. For every 1 gram of magnesium burned, 1.66 grams of the white powder is obtained. From this evidence we conclude that in burning, magnesium has combined with another substance (the oxygen), rather than " lost its celestial fire" or "phlogiston." The French chemist,
an atmosphere of oxygen,
is
Lavoisier, investigated the changes in weight arising
from com-
16
KINDS OF MATTER
TABLE
1
13
The Chemical Elements
14
bustion,
Ch.
and was thereby led to the first correct explanation of the process of combustion. 17. Classification of the Elements. The elements may be
the most
in various ways, according to one's purpose, but useful and far reaching classification is that furnished
classified
by
in families or
the Periodic System, whereby the elements are arranged groups based upon similarities in atomic structure
will
and chemical behavior. This arrangement in Chapters V, XVI, and XVII.
be explained
18. Symbols. Along with each element in the table is also a symbol used as an abbreviation of its name. It consists of the initial letter of the name, followed, where necessary to distinguish between several elements having the same initial, by a second appropriate letter. In many cases the symbol follows the Latin name of the element rather than the English name, allowing the symbols to be practically the same in all the principal languages. Thus, the symbol for iron is Fe, from the Latin ferrum; that for gold is Au, from the Latin aurum etc. These symbols stand, also, for the smallest particle of each element called an atom, each having an exceedingly small but definite weight, called its atomic weight. The numerical values of these atomic weights depend upon the units chosen. The values in the table are in terms of the arbitrary number of 16.000 given to the weight of an atom of oxyy
gen.
19.
Formulas
of
Compounds. Symbols are combined
in
formulas to denote the elementary atoms present in compounds. For example, NaCl is the formula of sodium chloride, common salt, and shows that it is made by combining sodium
atoms, Na, and chlorine atoms, Cl, in equal numbers. Again, Fe2Oa is the formula of ferric oxide, familiar as the ore, hematite, the pigment, Venetian red, and the pigment or polishing material, rouge, and shows that it contains iron (ferrum) and oxygen in the proportion of two atoms of iron to three of
oxygen.
By
late, further,
using the atomic weights in Table 1, we can calcuthe ratio of weights, as shown in the following
scheme.
21
KINDS OF MATTER
Ratio of atoms
1 1
15
Formula
Ratio of weights
atom atom
of
sodium
23.00 parts
by weight
of
sodium
of chlorine
2
35.46 parts by weight of chlorine
atoms of iron atoms

of
oxygen
X X
55.84 parts
16.00 parts
by weight
of iron
by weight of oxygen
These matters are explained and IV.

20. Molecules. If a substance
in detail in
Chapters
II,
III,
or can be
dissolved in
is a gas, or can be vaporized, an appropriate solvent without under-
going a chemical change, it is possible to determine, by experiments and deductions explained in Chapter IV, the groups of atoms, or molecules, which are capable of independent existence. One striking result is that the molecules of many elements do not consist of single atoms, but of various
numbers, as illustrated by:

Helium
Neon
Hydrogen
Nitrogen
Iodine
He Ne
H2
Oxygen Ozone
Phosphorus
(active form)
O2
Os
?4
Sg
N
h
Sulfur (in
solution)
21.
Molecular Weights. Molecules of compounds often are
multiples of the simple numbers of atoms that weight ratios alone would indicate, e.g., H2O2 hydrogen peroxide; C2H 2
acetylene; C 6 6 benzene. The last two contain the same ratio of carbon to hydrogen but differ in molecular weight.
Ratio of
weights
Molecular
weight
u^ HO
2
u A
hydrogen peroxide
H=
=
rr
rl
2
^
1.008
34.016
^^
C 2H 2
acetylene
j^
26.036
C6 H 6
benzene
~
l.UUo
78.108
16
Ch.
22. Kinds of Matter: Experimental Distinctions. We summarize the classification of materials presented in
may
this
chapter by the following scheme. It is not important to memorize it, but it is desirable to review the experimental distinctions that have been made in order to be sure that they
have been clearly understood.
Kinds
of Matter:
Heterogeneous. Separable by mechanical means into
Homogeneous.
Solutions. Separable
by
partial changes of state into
Pure Substances. Compounds. Separable by chemical reactions into

Elements.
23.
Kinds
of Matter: Theoretical Distinctions.

of
There
is
stating the above distinctions, one which way seeks to account for them in terms of the atomic-molecular
second
structure of matter. Although the statements of this structure in paragraphs 18-21 above are only very partial and preliminary, intended only to prepare the way for chapters that
most readers have already sufficient acquaintance with these things to make it worth while to restate the preceding scheme in these terms. Here again we have something to understand, structures to visualize, not simply a form to
follow,
'
memorize.
Kinds
of Matter:
Heterogeneous. Different kinds of visible regions separated by sharp boundaries. Homogeneous. Visually uniform throughout. Solutions. Different molecular species irregularly mixed. Pure Substances. Molecules all of one species.*
substance containing molecules of different species will also survive a partial change of state without separation of these separate species if they are in rapid equilibrium with each other. Sulfur, for example, is usually regarded as a pure substance, in spite of the fact that in the neighborhood of 200 C. liquid sulfur contains both octagonal molecules of S* and chain molecules of
1
varying lengths.
WtKjHIKbLAIIUINS
XI
3. The Law of Conservation of Mass is violated appreciably only in reactions in which new atoms are formed, involving enormous quantities of energy, in which cases it is the sum of the mass and
the energy that is unchanged. However, it takes enormous energy changes to have a detectable influence on mass, for 1 g. is equivalent
10 20 ergs. Another way of stating this is that 1 pound of mass is equivalent to 11,300,000,000 kilowatt hours. To make this relationship more real we may note that if 50 liters of hydrogen measured at 1 atmosphere and room temperature weighing 4.032
to 9
grams, were converted entirely into helium, the loss in mass would be 0.03 gram and the energy evolved would be 700,000,000 kilogram calories, enough heat to raise 7000 tons of water from freezing to boiling temperature. This heat is 5,000,000 times the amount that would be liberated in burning this same amount of hydrogen. Conversely, the heat lost in burning hydrogen, which is large as chemical reactions go, corresponds to a change far too small to detect on the most delicate balance.
of Definite Proportions. It was pointed out in that although there are many pairs of substances Chapter which can be "combined" to form solutions in continuously
4.
I
The Law
varying proportions, all solutions can be resolved into their pure components of constant composition by submitting them to fractional changes of state, including distillation,
crystallization,
of pure substances, coma striking fact which can hardly be explained except on the assumption of atoms combining in some simple, definite pattern. If matter were continuous, as it appears to the eye, it would be hard to see why elements could not be combined in continuously variable
and sublimation. The existence of vast numbers

is
pounds as well as elements,
proportions.
5.
The varying ways

is
in
tions"
stated indicate
which the "law of definite proporsome confusion with respect to it.
Here is one: "A chemical compound always consists of the same elements in the same proportions by weight. This statement can be reversed to give a clear definition of a chemical compound: a substance which has a definite composition by weight is a chemical compound." Now a critical
Ch.
II
student may well object to defining two things in terms of each other as merely going around in a circle. Also, he might ask, will not a particular sample of sea water "always" show
the same composition, year after year, if portions of it are drawn off and analyzed? The answer is, of course, yes. The composition of any particular solution is quite 'definite." Another statement of the law is: "The composition of a pure compound never varies." The joker in these statements lies
'
words "always" and "never." It is necessary to realize that something must have happened during the interval of time implied in these words, namely, one or more of the
in the
purification processes, natural or artificial, afforded by changes of state. The significant fact about the law of definite proportions is the existence of immense numbers of pure
compounds whose
properties, including composition, are identical for all samples from different sources. 6. The Law of Simple Multiple Proportions. There are
many
cases in which the
same elements combine
in different
weight ratios to form different compounds. The followihj* compounds of oxygen may be considered as examples:
TABLE
Other element
1
Per cent
oxygen
88.8
Wt.
Wt. oxvgen ottier element
Water Hydrogen
peroxide
7.94
> J
\
Hydrogen
Iron
94.1
15.88
= =
7.94 7.94
2X
Rouge
Lodestone
j
*]
30.06 27.64
7.167
.4298 .3820
Litharge Lead dioxide
>
Lead
Red
lead
13.375 9.264
0.0772 0.1544 0.1021
= 9 X = 8 X = 1 X = 2 X =4 X
0.04775 0.04775
0.0772 0.0772 0.0772
= = =
6 4
X X X
0.0257 0.0257 0.0257
The ratios of the weight of oxygen to the weight of the other element are- in each case simple multiples of each other, that is, one can be obtained from another by multiplying it by a small integer or by a fraction containing only small
integers.
The compounds of carbon with hydrogen are so numerous that larger numbers have to be used, but they
WEIGHT RELATIONS
23
too are always integers. The above are no isolated cases, for all experience shows that in all cases in which two or more compounds of the same elements exist, the amount of one
element combined with a fixed weight of the other in the different compounds can stand to each other in ratios of whole numbers, usually small. The picture of matter as composed of elementary atoms furnishes a complete explanation of the laws of definite and
multiple proportions, and
one ever
as
if
offered.
We can
could see them not enough to convince a sceptic there is still more evidence available, as will be set forth in Chapters XVI and XVIII. We would expect certain simple combinations of unlike atoms to be the stable ones, giving "definite," reproducible proportions, and, if additional combinations are possible, they too should be simple, and hence simple multiples of the first. The water molecule was for a long time thought to have the formula HO, but we now know, for reasons to be explained later, that it is H 2 O. If hydrogen peroxide is HO or H 2 O 2 it explains the figures in Table 1. (The true
table
is
,
we
indeed, the only reasonable as sure of the existence of atoms with the naked eye, for if the above
is,
feel
formula
is
H 2O
2,
as
we
shall see in
,
Chapter IV.) Litharge

is
is is
PbO,
also a
lead dioxide
is
PbO 2 and
red lead
Pb3 O 4 (There
.
Pb 2 and Pb 2 O 3 .) Rouge is Fe 2 O 3 and lodestone is Fe 3 O 4 The weight ratios given in Table 1 all agree with these formulas when combined with the atomic weights,
.
Chapter
I,
Table
1.
Thus,
Fe 2 O
Fe,O4
Wt
y*
3
2
Wt. iron
X X
16
4
0.4298
3
55.84
X X
16
0.3820
55.8
correct ones
have not yet proved that the above formulas are the and give them only to show that simple atomic formulas can yield the simple multiple relations observed. 7. The smallest group of atoms that can exist isolated from other like groups, as in a gas or in solution, is called a molecule. The molecule of a compound contains more than
We
24
Ch.
II
one kind of atom. The molecule of an element consists of one or more like atoms. The atoms of the elements are designated by the symbols given in the table on page 16. For example, H denotes an atom of hydrogen. In hydrogen gas, a pair of atoms forms a molecule, designated H 2 Similarly the oxygen atom is O and the molecule is O2 A molecule of water is designated by the formula, H 2 0, indicating that it contains two atoms of hydrogen and one atom of oxygen. The evidence for these formulas will be presented later, our
.
purpose at present being merely to explain the significance of chemical symbols and formulas. 8. Numerical Values of Atomic Weights. The actual weights of the atoms are exceedingly small, expressed in ordinary units, such as grams, and it is far more convenient to select a much smaller weight as unit, such as the weight of one of the atoms themselves. It is purely arbitrary which atom we choose and what number we assign to it, so long as we select corresponding values for the other atoms. Thus, knowing that the molecule of water contains 7.94 times as much oxygen as hydrogen, and granting that H 2 is the correct formula for it, we might call O = 100, when H would = 0.0630, etc. be 6.30, or again, if we let O = 1, then
The choice appeared a very simple one to most early chemists, who, finding that the atom of hydrogen is lighter than that of any other known element, decided to call its weight 1, corresponding to atomic weights greater than one for all other elements. Later it was found that the ratio of weights of the atoms of hydrogen and oxygen is not exactly 1 to 16, but 1 to 15.88, and that if we take O = 16.00 as our unit, making H = 1.008, the atomic weights of most of the other elements come out much nearer whole numbers than if we let H = 1 and O = 15.88. This is illustrated by the following sets of values based on the two assumptions.
Hydrogen Oxygen
Calcium Carbon Lithium
1.008
16.00
1.000
15.88
39.76 11.91
40.08
12.01
6.94
6.89
10
WEIGHT RELATIONS
Magnesium
Nitrogen
24.32
14.01
85
24.13 13.90
30.77
Phosphorus Potassium
31.02
39.10
23.00
38.80
22.83
Sodium
Sulfur
32.06
31.82
An
additional reason for the choice of
O =
16.00
lies
in the
few of the elements form compounds with hydrogen, while nearly all form compounds with oxygen, and hence the atomic weight ratio between an element and oxygen can be determined directly, while the atomic weight ratio between the element and hydrogen could only be determined indirectly, and would therefore be subject to greater error.
fact that but
9.
The numerical
values of the atomic weights permit us
to extend the meanings of chemical formulas to include the ratios of weights of the elements contained in compounds.
For example, the formula, CO 2 indicates not only a molecule of carbon dioxide, composed of one atom of carbon and two atoms of oxygen, but since an atom of carbon weighs 12,
,
the weight of an atom of oxygen is called 16, the molecule weighs 44 and contains 12 parts by weight of carbon and 32 parts by weight of oxygen. Furthermore, since this proif
wt. carbon
portion,
12
,
wt. oxygen
32
for
applies to
,.
any molecule
..
of
CO 2
_._
.
,
it
applies to
any number of molecules and to any units of weight.
Hence we can write
CO 2
Wt. carbon _ 12 atomic wt. 32 atomic wt. Wt. oxygen
units
units
__
12 g.
12
Ib. Ib.
32
g.
32
12 oz.
1.000 g.
etc.
32 oz.
2.667 g/
10. It is convenient to let the symbol of an element stand not only for one atom, but, alternatively, for one gram-atom, which is that quantity of the element whose weight in grams is numerically equal to the atomic weight. Since atoms are so small as to be invisible through the most powerful micro-
26
scope,
Ch.lt
it is evident that the number of atoms in a gram-atom must be an extremely large number. There are, fortunately, several independent methods for determining it, all of which
agree within their own limits of error. The best value at 23 atoms to have the present is that it takes 6.023 X 10
weight of
Number,
in
gram-atom. This number is called the Avogadro honor of the Italian physicist who discovered
the principle that bears his name (cf. Chapter III, paragraph 20) and dispelled the confusion that once existed regarding atomic weights and formulas. The relation between atoms
and gram-atoms
is
illustrated in
Table
2.
TABLE 2
Weight of
1
atom
Weight of
1
In atomic
weight units
In grams*
2.66
or 6.023
gram-atom, 10 23 atoms
Oxygen Hydrogen Copper Gold

*
16.00 1.008
0.167
10.6
63.57
197.2
32.7
X X X X
10~ 23 10~ 23 10~ 23 10~ 23
16.00
1.008
grams
"
63.57
197.2
The student who has forgotten the significance of the use of exponents fot expressing very large and very small numbers would do well to get it clear, ai we shall make frequent use of it. The following relations should help: 10~ 3 = 1/10 3 = 1/1000 = 0.001, 10 3 - 10 X 10 X 10 = 1000, 3 X 10- 4 == 0.0003, 10 = 1, 5 X 10 4 = 50,000, 2 X 10~ 23 = 0.000,000,000,000,000,000,000,02, etc.
manner, the formula of a molecule can stand, 23 alternatively, for 6.023 X 10 molecules, called a grammolecule or mole, whose weight in grams is numerically equal to its molecular weight. For example, the formula, CO 2
11. In like
,
in
addition to standing for

it,
molecule, whose molecular
weight
of
is 44 atomic weight units, can also stand for 44 grams which quantity contains 6.023 X 10 23 molecules.
12.
There are several ways of determining the Avogadro Number,
the easiest to comprehend probably being the following. It is possible to measure the electric charge of a single atom or particle
of negative electricity, called an electron, in the following way, devised and carried out with great ingenuity by Dr. Robert A. Millikan, who received a Nobel Prize for his work. The method
13
WEIGHT RELATIONS
27
consists in holding a minute drop of oil, charged negatively by having acquired one or several electrons, suspended in an electric
field just sufficient to
is
neutralize the effect of gravity.
The apparatus
shown in simplified form in Fig. 1. Oil drops are blown into the upper chamber by an atomizer and one has fallen through the hole in the bottom into the space between the two metal plates where it can be observed by a microscope. Electrons are produced by
letting
X-rays enter the chamber. When the oil drop has picked an electron it can be kept from further falling by applying the up
Atomizer
Condenser
plates
Scale
Telescope
Fig. 1.
Apparatus for determining the elementary charge.
proper charge to the electric plates, the upper one made positive. In order to determine the weight of the drop, which just balances the electric force, the charge on the plates is removed and the velocity observed as the drop falls. An equation, known as Stokes'
Law, permits the calculation
of the radius of the drop, therefore its
weight, from the velocity of fall and the density of the oil. The gravitational force on the drop gives, in turn, the electrical force which balances it, and from the known electrical charge on the plates the charge on the drop is calculated. It turns out to be 1.6020 X 10~ 19 coulombs or some integral multiple thereof. This furnishes the most convincing proof of the atomic nature of electricity. It
makes
it
possible, also, to calculate
Avogadro's Number,
takes 96,500 coulombs of electricity to deposit enough hydrogen atoms to give 1.008 grams of hydrogen, which is 1 gram-atom of it, and 96,500 4- 1.6020 X 10~ w gives 6.023 X 10 23
for
it
.
The most accurate method Number is to compare the angle of

13.
of determining the Avogadro diffraction of X-rays of definite
wave length by a
Ch.
II
grating whose lines are a known distance apart with the diffraction of the same X-rays by the atoms in a certain comparison of the two angles of diffraction permits the crystal.
calculation of the
of the crystal, substance by the aid of
number of atoms per centimeter along the edge and knowing the volume of a mole of the crystal
its
density,
it is
possible to calculate the
number
of
atoms
it
contains.
this clear to the reader unfamiliar
Figure 2 should
make
with the
diffraction grating. Parallel light of single wave length X-rays coming from left to right strikes a grating consisting of opaque
which the
portions of uniform length, d, with openings between them through light can pass. Most of the light passes on in the original
direction after leaving the grating, but some of it is bent, or diffracted, at an angle, 6, such that the difference in path, /, is equal to
one
full
wave
length,
where the
rays can again fit crest to crest (there are other beams at angles
such that
lengths). If we value of d from the
wave
equals two or more know the
way
the
grating was ruled, and measure 6, we can calculate the wave

length of the X-fays
relation sin 6
/
from the
l/d. If
we now
substitute a crystal, where d' is the distance apart of the atoms,

Fig. 2. relation
between
Diffraction of light or X-rays; angle of diffraction,
wave
d'.
length,
and grating
of
distance.
and measure a new angle, 0', since we know / for the X-ray S J being used we can calculate
atoms per cm. is then l/d'. If the crystal is salt, NaCl, molal weight 58.46 g. and density simple cubic, e.g., a mole cube would have a volume of 27.00 cc. with 3.0 cm. 2.163, on each edge. The number of atoms (ions) along each edge would be 3.0/d' and the number in the cube would be (3.0/d') 3 which would be twice the Avogadro Number.
rock
14. Weight Relations from Formulas. Let us at this point consider a sample calculation of the sort that we now have the basis for making. Suppose that we wish to calculate the
The number
amount
of lead required to
make 100 grams
of red lead,
15
WEIGHT RELATIONS
.
29
Pb3 O 4
we
3 3
whereby
will assume that some process can be found the lead taken can be turned into Pb 3 O 4 hence can write the following series of logical steps.
all
,
We
atoms
of
Pb
gram-atoms
cule of
of
are required to produce 1 molecule of PbaO 4 Pb are required to produce 1 gram-mole.

.
Pb3 O 4
are required to produce (3 (4 X 16) grams of Pb 3 O 4 621 grams of Pb are required to produce 685 grams of
207 grams of
Pb
207)
.
Pb3 O 4
.
ff\
685
100
grams of Pb are required to produce

/ô
1
gram
of
Pb3 O 4
Ooo
= grams
4.
of
Pb
required to produce 100 grams of
Pb3
90.7
grams
of
Pb
required to produce 100 grams of

briefer
Pb3 O 4
of expressing the solution would be to state explicitly the idea of the proportionality of 3 Pb to Pb 3 4 regardless of the amounts of the units used,
An
alternative
and
method
as follows:
Wt.
whence
lead
4
=
~~
207
g.
g.
~ =
g.
g.'
Wt. Pb 3
685
100
100
*
15.
:
X
685
621
= on 9a7g
'
is much used in books on chemistry, This too readily becomes a purely formal procedure, the basis for which is often not understood by the student; there is nothing in it as written to show why it should not be 685 621 :x 100; and it is likely to be worked by a rule divorced from ordinary algebraic procedure. It is highly desirable to be freed as much as possible from mere rules, blindly accepted. A person may be trained to rival a computing machine in carrying out operations by some sort of formal procedure that he does not understand, but if he is to be educated he must learn how to anlayze
third form
: :
685
621
100
x.
30
Ch.
II
problems for himself, starting from the pertinent data given his command; obtaining a clear view of the answer desired, which is the objective; and proceeding towards it by a series of logical steps, like a man crossing a stream by a series of stepping stones. The first method given above is a sample of such a series of steps, chosen to require very
and at
small logical jumps; many persons could take bigger ones. But this, like the second, and logically equivalent one, indicates the reasoning involved, simple as it is. The steps can be easily checked and the units are shown.
Chemical Equations. When a chemical reaction takes there is a rearrangement of atoms into new groups, 01 place molecules, forming new substances. This is indicated by a chemical equation, in which the rearrangement is shown by
16.
the regrouping of the atomic symbols to represent the new molecular species formed. For example, the formation of iron and carbon dioxide, CO 2 from the ore Fe 2 O 3 by the action of carbon monoxide, CO, is represented by the equation
,
Fe 2 O 3
+ 3CO =
2Fe
+ 3CO
2.
may be noted about such ,an equation an equation states nothing about the conditions First, necessary for carrying out the reaction, and the mere writing of an equation does not imply that the reaction it represents can actually be realized. Second, it must represent the fact that no matter disappears, by showing the same number of atoms of each element on both sides of the equation, though they are
following facts
:
The
arranged in different molecules. Third, it represents the relative number of molecules of each substance taking part in the reaction. Fourth, it represents the relative weights of each substance, which can be readily computed with the aid of the table of atomic weights. The above equation, then, may be read as follows: 1 molecule of ferric oxide reacts with 3 molecules of carbon monoxide to yield 2 molecules (or atoms) of iron and 3 molecules of
17
WEIGHT RELATIONS
31
carbon dioxide; also, of iron oxide react with 3(12 56 parts of iron to give 2
2x56 + 3x16
-f-
parts (by weight)
16) parts of carbon
monoxide
and 3(12
dioxide.
unit,
These parts by weight
may
32) parts of carbon be in any kind of weight
pounds, tons, ounces, grams, etc. In accordance with our double usage of the symbols and formulas to represent not only single atoms and molecules, but also gram-atoms and gram-molecules, or moles, as explained on page 26, we often read an equation in terms of grams; hence, 160 g. of iron oxide, when reacting with 84 g. of carbon monoxide, give 112 g. of iron and 132 g. of carbon dioxide, which quantities represent 1 mole, 3 moles, 2 moles, and 3 moles respectively. This may be summarized briefly by writing under each formula in the equation its complete meaning in both of the above senses. Fe2 O 3 + SCO - 2Fe -f 3CO*
(1)
Number
of molecules
(2)
Weight, in terms of onesixteenth the weight of an oxygen atom Number of moles
132
84
g.
160
160
Weight
17. Calculation of
1323
112
132 132
84
g.
112
g.
g.
attached to chemical formulas

sible to calculate the
Weight Relations. The meaning thus and equations makes it posweights of

all
the other substances involved in a chemical reaction from the weight given for any one of them. Suppose, for example, that it is required to find the weight of iron that should be obtained from
100
Ib.
of the oxide of iron considered above.
weights implied by the formulas, as explained may write the following:
From the above, we
160 160
g. of
Ib.
of
Fe 2 O 3 gives 112 g. of Fe. Fe 2 O3 gives 112 Ib. of Fe.
1 Ib. of
Fe2 O3 gives
112
Ib.
of Fe.
loU
10
100
Ib.
of
Fe2
*
160
112
gives
70
Ib.
of Fe.
3*
Ch.
II
Again, suppose we wish to find the amount of coke, containing 80 per cent carbon, the rest being ash, that is required to reduce to iron the above amount of ore. From the weights
implied in the equation,
1
we can say
that
requires
mole Fe 2 O3 requires 3 moles 3 gram-atoms of C.

Ib.
CO, which
160 100
Fe 2 O 3 requires 36
Ib.
C.
Ib.
Fe 2 O 3 requires
^X
100
36
80
22.5 Ib. C.
160
22.5 Ib.
is
80 per cent or
luu
of the coke required,
which
is
80
22.5 Ib.
28.1 Ib.
This connection between atomic weights, formulas, and

relative weights of substances may be used not only to calculate the relative weights from the formulas and atomic
when the formulas and
weights, as above, but also to calculate the atomic weights suitable weight relations are known,
or again, to determine formulas are known.

18. Calculation of
when the other two
factors
Atomic Weights. As an example of the
calculation of atomic weights let us suppose that we know the formula of a certain oxide of copper to be Cu 2 O and
on analysis that 0.5120 g. of it contains 0.4548 g. of copper, and wish to calculate the atomic weight of copper,
find
provisionally called x. reasoning as follows:
We may
Cu 2O
0.512
g.
arrange the steps in the
Given by formula Given weights, by analysis Given relative no. gram-atoms from formula Wts. in 1 mole of Cu2O from
formula Wts. in 1 mole of Cu2<3 from
analysis
contains
Cu
and
g.
0.4548
2
0.0572 g.
1
2x
g.
16
g.
'
4548
&
16
19
WEIGHT RELATIONS
last
33
Comparing the
two
figures in the
column
for
both represent the copper combined with 16 hence they are equal, and
2X
g. of
t
copper oxygen,
0^72
'
4548 g "
63 6 g "
'
hence the atomic weight of copper is 63.6. 19. Calculation of Formulas. The third case consists in calculating the formula when the other two factors, atomic
weight and composition, are known. Suppose that we find on analysis that a certain chloride of arsenic contains 58.68 per cent of chlorine, and know the atomic weight of arsenic, As = 74.91, and chlorine, Cl = 35.46, and wish to determine
the formula of the compound. Now the formula indicates the number of atoms, or of gram-atoms, in the molecule, or mole, repectively, so that we may proceed to determine the
number of gram-atoms atom of the other.

of
of
one element combined with

g.
gram-
Given, 58.68 g. Cl combine with 41.32 compound, then

35.46 g. Cl combine with
As
to yield 100.0 g.
^^ X
58.68
2 C A /C
41.32
'
24.970
g.
As,
or
gram-atom
Cl,
combine with
24.97
0.3334 or almost
exactly \ gram-atom As (analyses are, of course, subject to small errors), or 3 gram-atoms Cl combine with 1 gram-atom As, and 3 atoms Cl combine with 1 atom As; therefore the
simplest possible formula
is
AsCl 3
,
The above
satisfied
weight relations would, however, be equally
by the formulas As2 Cl G AsaClo, etc., and before deciding upon AsCl 3 we shall have to determine the weight of 1 mole, for 1 mole of AsCl 3 would weight 181.23 g., while 1 mole of As2 Cl 6 would weigh twice as much. (Chapter IV deals with
the problem of molecular weights.) The simplest formula that fits the figures obtained from analysis is often called the empirical formula, the word
34
Ch.
II
"empirical" meaning based on experiment or experience rather than upon theory, or full scientific knowledge. In this case, however, the experiment is incomplete, calling for further experiment to determine molecular weight. 20. The foregoing examples and the tabulation at the end of
paragraph 16 all show the great numerical simplicity achieved in chemical calculations by using moles and gram-atoms instead of ordinary units of mass, such as grams or pounds. The
student will do well, therefore, to overcome a natural reluctance to work with a new, unfamiliar unit, and to adopt the common practice of chemists of expressing quantities of pure
substances in terms of these chemical units.
Exercises
See Appendix 2 for answers.

1.
What do you
understand by the law of simple multiple
proportions? 2. How does the atomic theory explain this law?

3.
Write out
in
;
words
all
;
that the following formulas

.
mean
to
you:
4.
O;
HO
2
Ca(OH) 2 FeSO 4
Define symbol, formula, chemical reaction,, chemical equamole, molecule, atom. tion,
5.
6.
7.
How many atoms of oxygen are in 1 molecule of Ca(OH) ? How many gram-atoms of lead (Pb) are in 2 moles of Pb O ? How many gram-atoms of oxygen would be used up in
2
3
converting
8.
gram-atom
of lead into
Pb 304?
2
PbO 2
can be made from Pb 3O 4 by the reaction:
Pb 3O 4
3
+ 4 H+ =
PbO 2
+2HO+
2
Pb++.
How many pounds of PbO 2 could be obtained from 100 Ib. of Pb O 4 ? 9. How many gram-atoms of sulfur are there in 196 g. of sulfuric
acid,
10.
H SO
2
4?
What
weight of water could be obtained from 1.00
g.
of
Cu 2O?
11. How much water would be required to convert 100 g. of phosphorus pentoxide, P2Os, into phosphoric acid, the equation
being: 3
HO+ PO =
2
H PO
3
4?
WEIGHT RELATIONS
12.
13.
35
weight of aluminum, Al, must be used per kilogram 3 Fe 3 O 4 of iron oxide, Fe 3 O 4 to carry out the reaction: 8 Al
,
What What
per cent of A1 2O 3
is
aluminum?
4A1 2O 3
14.
+
2
9Fe?
When
yields
treated with hydrochloric acid, barium peroxide hydrogen peroxide according to the following equation:
BaO 2
make
a 5 per cent solution of H 2O 2 ? 15. What weight of aluminum could be dissolved by 196 g. of sulfuric acid, H 2 SO 4 ? The equation is: 2 Al + 3 H 2 SO 4 = A1 2 (SO 4 ) 3
10
Ib. of
HC1 =
HO +
2 2
BaCl 2
How much BaO
is
required to
+ 3H
16.
2.
What
of
grams 2 Fe 2O 3
17.
weight of Fe 2O 3 would result upon burning 10 kiloFeS 2 ? The equation for the reaction is: 4 FeS 2 + 11 O 2 =
8
SO 2
oxygen only was found and 3.00 g. of oxygen. (a) How many grams of oxygen, (6) how many gram-atoms of oxygen would be combined with one gram-atom of sulfur in this
by
certain compound of sulfur and analysis to contain 2.00 g. of sulfur
compound?
18. Since engineers use the avoirdupois units, including
pounds,
possible to use pound-atoms and pound-molecules. Define them, give their relation to gram-atoms and gram-molecules, and calculate the number of atoms in a poundunits, it
is
more often than metric
atom.
(1 Ib.
453.6 g.)
CHAPTER
III
THE KINETIC THEORY

Properties of Gases. While we are discussing the general properties of substances it will be profitable to consider certain properties of gases, on account of the existence
1.
Common
of important uniformities in their behavior from which we can learn much about molecules. When solids and liquids are heated, they expand, in nearly all cases, but the rate of expansion with the temperature is a specific property of each
The same holds true for the compressibility oi and liquids. With gases, however, the effect upon the volume of changing temperature or pressure is nearly independent of the particular gas used. This is illustrated by the accompanying table.
substance.
solids
TABLE
Increase in
1
Volume When
Gases
Cubic Centimeter of Material at
C.
Is
Heated
to
C.
Liquids
Acetylene
Ammonia
Argon Carbon monoxide
Chlorine
0.003,77 .003,75 .003,68

.003,67
Alcohol
Chloroform Ether
0.001,05 .001,21
.001,56
.000,18
.003,90
Mercury Water
Solids
salt
.000,06
Helium Hydrogen Methane Oxygen
.003,66 .003,66
.003,68
Common
Copper
.000,032
.000,017 .000,000,27
.003,66
Diamond
compressibility,
Similar regularity with gases is evident on examining the the relative decrease in volume on i.e.,
applying pressure.
further distinction between gases, on one hand, and liquids and solids, on the other, is their tendency to expand indefinitely, so as to fill completely any space at their dis36
THE KINETIC THEORY
37
posal, always exerting pressure vessel.
on the walls of the containing
Again, the rate of diffusion of one gas through another is vastly more rapid than diffusion through a liquid or through a solid, in which case, indeed, measurable diffusion is very
as illustrated by sharp boundaries in rocks between minerals which have been in contact for millions of years. 2. Now these characteristics of gases are such as to excite
rare,
the curiosity of persons having the scientific attitude as to why gases behave as they do. We may also wish to be in a position to predict more accurately than we can from the
above meager information how they behave. The former question is theoretical, the latter immediately practical. We may choose to begin by speculating regarding the answer to the former, or by performing a series of careful experiments
to reveal the latter.
The former course should
yield a theory,
the latter the "gas laws." Science advances by using either avenue of approach, now the one, now the other, or both
together.
The student might, at this point, go into the laboratory and work out by well-controlled experiments the relations
3.
between pressure, volume, temperature, mass, and molecular weight of one gas; satisfy himself that the formulas obtained are applicable to a number of gases and hence, probably, to all gases. This is the inductive approach already referred to in Chapter II; it starts with particular cases and leads up to general laws which are. essentially descriptions of behavior.
The other approach
is to construct some theory, model, or of the possible structure of gases in this case, from picture, which the behavior of individual gases could be inferred by
of course, be tested
deduction. All the various consequences of the theory should, by experiment before it should be given
any great
scientific standing.
will be emphaa powerful tool for dealing with other more complicated matters, such as the control of chemical reactions. If it were merely a question
4. In the present case, the latter
approach
is
sized because the resulting theory
38
Ch.
Ill
of gas behavior,
we might leave the whole matter to the but the theory is of such value to chemists, and physicists, so illuminating, indeed, to anyone interested in his physical environment that practice in working it into one's active imagination is rather sure to be rewarding. It is, at least, a
labor saver, for it leads so obviously to the correct arithmetical treatment of gas problems as to make it unnecessary to commit to memory formulas almost certain to be misapplied
or forgotten. 5. Let us ask the question. What sort of structure must gases possess in order to account for their general properties? The most satisfactory picture is that furnished by the Kinetic
Theory, which assumes that a gas is composed of particles called molecules, whose size is very small compared with the distance between them, and that each molecule is in rapid motion, colliding with other molecules and with the walls of the containing vessel. 1 It is these impacts which produce the observed pressure, a rapid series of impacts obviously having the effect of a steady pressure. The further assumption is made that the average velocity of the molecules, and hence
the pressure produced upon the walls of the vessel, depends upon the temperature, increasing as the latter increases.
The molecules
are in such rapid motion, and are most of the time so far apart, relatively, that their mutual attractions
have very little effect. This picture of the condition of gases has proved to be of such immense service in explaining and predicting their
properties that present time.
it
is
hardly questioned by scientists at the
6. Relation between Quantity and Pressure When Volume and Temperature Are Constant. Let us see first, how, on the
basis of the theory just given,

1
we should expect changes

may
f
in
An
idea of the actual values calculated
be obtained from the following
C. one cubic centimeter figures for oxygen. At one atmosphere pressure and of oxygen contains 27 10 18 molecules, moving with an average velocity of
0.46 kilometer per second (about i mile per second). Each molecule travels on an average about 1000 times its own diameter before colliding with another molecule.
86
THE KINETIC THEORY
39
the amount of a gas to be related numerically to changes in pressure. Imagine a gas inclosed in a vessel provided with
a cock, as represented in Fig. la. The vessel is supposed to be immersed in a bath to preserve constant temperature. Let us have very few molecules in the vessel, and visualize them by the dots in the figure. These molecules will all be in rapid
rectilinear motion, some moving faster, some more slowly, between impacts, but with a certain average velocity depending on the temperature, producing a definite pressure on the vessel walls as they rebound 'fl from them. Suppose, now, that we introduce an equal number
of the
same kind
of molecules
through the valve, producing the condition illustrated in Fig. Ib. It is obvious that
since the
volume
of the vessel
remains the same, and the
F j average speed of the molecules is kept the same by the action of the bath in maintaining constant temperature, the only effect of the doubling of the amount of gas is merely to double the number of impacts in a given time per unit of area of the vessel walls, and hence
to double the pressure. Evidently we would expect any change in the number of molecules in the vessel to produce a proportional change in the pressure, and since the number
of molecules
depends on the amount of the
gas,
we can make
the general deduction that when temperature and volume are kept constant the pressure of a gas is proportional to the quantity present. As an example of how this may be applied let us consider
a tank, with an attached pressure gauge, containing any gas. Allow the gas to escape until the pressure falls from 100 Ib. per square inch to 30 Ib. It is evident, since the pressure has fallen to 0.3 of its initial value, that there remains in the tank
only 0.3 of the gas originally present. Many pressure gauges give, not the absolute pressure, upon which this discussion
40
is
Ch.
Ill
based, but only the excess over atmospheric pressure. is a tire pressure gauge, reading zero, not when the pressure is zero but when it is the same as the
familiar example
outside atmospheric pressure, which is 14.7 Ib. per square inch. If the pressure given in the above problem was not the absolute pressure but the differential pressure, as read on such a gauge, then the true pressures inside the tank were
per square inch before release and 44.7 Ib. per inch after release, and the amount of gas remaining square in the tank after release was 44.7/114.7 or 0.380 of the original amount. In what follows, pressure always is intended to mean
114.7
Ib.
the true, or absolute pressure, not the net pressure. 7. Relation between Pressure and Volume When Temperature and Amount Are Constant. Let us imagine, next, that the gas is contained in a cylinder like that of a steam
|0
engine, with a movable piston, as in Fig. 2, so that the volume

\2p
of the inclosed gas may be altered without changing the
amount.
If, now, the piston is pushed down from the position
a
Fig. 2.
represented by a, in the figure, to that represented by b, where the volume is half as
and volume
Relation between pressure great, the of a fixed quantity of gas at on a R } ven constant temperature. . .
number
area Q f
.
of impacts
t [ie
,
wa
l| s J
,
n
,
a given time will be doubled. While the piston is being pushed down, the molecules striking it will rebound a little faster than before, causing a slight 1 increase in temperature, so that we must wait a moment till this temperature has been lowered to that of the bath surrounding the cylinder, when the average speed of the molecules will be the same as before the piston was pushed down. Since the number of impacts on a given area of the walls has been doubled, the pressure is likewise twice what
1 This effect automobile tire
may be
is
pumped
noticed in the heating of the up.
pump when
a bicycle or
9
it
THE KINETIC THEORY

was before the piston was moved. Evidently,
first,
41
were made one third as great as at
become three times as

in general that
great, etc.,
if the volume the pressure would so that we may conclude
the temperature and amount of gas are constant the pressure is inversely proportional to the
when
volume. This is usually called Boyle's Law. As an example, let us calculate the final volume when 10 1. of gas at a pressure of 76 cm. of mercury is subjected to a pressure of 19 cm. Since the pressure is decreased in the ratio 19/76, the volume will be increased in the same ratio,
becoming seventy-six nineteenths of
10
1.,
the
original
volume, or 40 1. 8. Relation between Pressure and Concentration
When
Temperature to the volume
Is Constant.
in
The
it
ratio of the
amount
of material
which
unit volume, concentration which determines the number of impacts, and hence the pressure, so long as the speed of the molecules is
unaltered.
If,
is called its
is contained, or the amount in concentration. Evidently it is the
for example, 2 g. of a certain gas in 5
1.
exerted
a pressure of 2 atmospheres, then 1 g. of the same gas at the same temperature in a volume of 10 1. would be only one
fourth as concentrated, and would exert only one fourth of the pressure, which would be one half atmosphere. In general, we may say that the pressure of a gas is proportional to its
the temperature is constant. 9. Relation between the Pressure, Mass, and Speed of the Molecules. Although, as has been said, the pressure exerted by a gas depends upon the velocity of its molecules,
concentration
when
not directly proportional to the speed, for if the speed is doubled, not only does each molecule hit the vessel walls twice as often, but also twice as hard, for the momentum of each molecule is doubled by doubling the speed. The pressure is thus proportional to the square of the average velocity of the molecules. Moreover, the change of momentum at each impact is proportional to the mass of the molecules. A heavy molecule would exert more pressure than would a light one moving at the same speed; hence, the contribution of a single
it is
42
Ch.
Ill
molecule to the pressure of the gas is proportional both to mass, which we will call m, and to the square of its velocity, 2 2 which we will call u, that is, to mu Now ^ mu is kinetic energy, so we can say that the contribution of a single moleits
.
cule to the pressure of a quantity of gas depends upon its kinetic energy. In a mixture of gases, the different species of
molecules must have the same average kinetic energy, since they tend to equalize kinetic energies by collisions. It is evident, therefore, that light molecules, like those of hydrogen,
must move much

oxygen
(cf.
faster
than heavier ones,
like
those of
paragraph 23). Temperature, When Amount Is Constant. Let us next see how a fixed quantity of a gas would be affected by a change in the temperature. It will be simplest, first, to consider the effect of this change upon the pressure and volume separately, keeping one constant while the other is allowed to vary. We will imagine a constant weight on the
10. Effect of
piston of the cylinder containing the gas, so that the volume may vary while the pressure remains the same. We may now vary the
'
temperature by altering that of the bath in which the cylinder is immersed. If the temperature of the gas is increased, we would expect, in terms of our theory,
that the molecules would gain in kinetic energy, moving faster and hitting the vessel walls and the piston both harder and
more frequently, forcing the latter upwards until the reduction in the number of impacts in a given time compensates
for the greater force of each impact. It is found by experiment that this increase in volume is uniform, as expressed by the
plot in Fig. 3. '11. Absolute Zero of Temperature. Similarly, if the piston is not permitted to move, so that the volume remains constant,
an increase
in
kinetic energy of the molecules,
temperature would be expected to increase the resulting in harder and
11
THE KINETIC THEORY
43
more frequent impacts, and hence an
increase in pressure.
The pressure of a gas at any temperature depends upon the amount of gas and its volume, i.e., its concentration, but
any given concentration the pressure increases uniformly with temperature, as shown in Fig. 4 for three concentrations. By careful measurements the increase is found to amount to
for
^3
in temperature.
C. for each degree rise of the value of the pressure at are led naturally to inquire the effect of
We
-273C
oc
273K
Fig.
tc
(273 +t) K
0K
a continued decrease in temperature. Diminishing the presC. for every degree the temperature sure -%Y^ of its value at 273 C. (more is lowered would give no pressure at all at 273.15 C.) if the gas did not condense to a exactly,
liquid
somewhere along the

in
line.
terms of the kinetic theory? Since What does this mean we have attributed gas pressure to the impacts of gas molecules moving with an energy depending on the temperature, when the pressure becomes zero we must conclude that the molecules are no longer in motion, and that we have reached the Absolute Zero of temperature. A lower temperature is inconceivable in terms of our theory. This remarkable conclusion is confirmed by the behavior of other properties, many
of which approach either zero or infinity, as the temperature 273 C. approaches
It is
both
logical, therefore,
and
for
many scientific purposes
more convenient,
to reckon temperature from the absolute
44
zero,
which
is
Ch.
Ill
below the centigrade zero. We denote K for Lord Kelvin. On this scale C, is + 273 K.; 17 C. is 273 + or 290 K., and in general, letting T and / stand for tem17, perature on the absolute and centigrade scales respectively, T = t + 273. The most convenient way of expressing the effect of temperature on the pressure is to say that wh^n the amount and volume of a gas are kept constant, the pressure is proportional to the absolute temperature, since both
273
absolute temperature by the melting point of ice,
depend upon the kinetic energy of the molecules. Figure 5 expresses in graphic form the relation between
four temperature scales: centigrade, Fahrenheit, absolute or Kelvin, which uses centigrade degrees, and Rankine, also counting from absolute zero but in Fahrenheit degrees. J2. As an example, let us find the final pressure produced
when a tank
291
of gas under a pressure of 10 atmospheres cooled from 40 C. to 18 C. 40 C. is 313 K., and 18 C.
is
is
K. Since the absolute temperature has been lowered to fy of its initial value, the kinetic energy of the molecules will be lowered to \\\ of its initial value, and hence the
pressure will be lowered to the same fraction of its initial value, which is ffi of 10 atmospheres, or 9.3 atmospheres. When the amount of gas and the pressure are kept constant,
temperature, with its proportionate energy of the molecules, must be comchange pensated by a proportionate change in volume. Suppose, for example, that we have 250 cc. of gas at 27 C., and wish to determine at what temperature the volume will
any change
in the absolute
in the kinetic
become 200
cc.
The new volume
will
be %%%, or 0.8 of the
old volume; hence the absolute temperature will be reduced to 0.8 of its initial value, or from 300 K. to 240 K., which is 33 C.
When Amount
Changing Both Temperature and Pressure, Gas Is Constant. When any two of the factors pressure, temperature, and volume are changed, the effect on the third can be calculated by separating the process into two steps similar to the above. For example, suppose
13. Effect of
of
THE KINETIC THEORY

H2O 180F above freezing
45
Boiling point,
(
point)
Body temperature
_ laboratory experiments
_ Melting point, ice
Boiling point,
NH 3
Sublimation point,
COf
Boiling point,
_ Boiling point,
H2
Absolute zero
Centigrade
Kelvin
Rankine
Fahrenheit
Absolute scales
Centigrade
Fahrenheit
degrees
Fig. 5.
degrees
Temperature
scales.
46
Ch.
Ill
we have
50.0 cc. of gas at 74 cm. pressure and 20 C., and wish to know the volume it would occupy under standard conditions, which are 1 atmosphere (76 cm. of mercury) and
final value, since the volume will be diminished to the pressure increased, of 50.0 cc. Next, keeping the pressure constant, let us
C. If
we
first
is
change the pressure to the
^
is
change the temperature from 20 C., which is 293 K., to C., or 273 K. This will cause a further diminution in volume in the ratio f |~f so that the result of both changes
,
fH X
HX
50.0
cc.,
or 45.3 cc.
14. The several gas laws which we have just deduced from the kinetic theory, and which are found to be in accord with
experiment, may be expressed by algebraic equations, and may be combined into one fundamental general equation.
When
one has to apply the gas laws frequently, it is wise to use equations, as the mathematical expression of a law makes it easier to use. As has been said, "a mathematical equation is a substitute for thought"; it enables one to represent briefly the result of thought, so that the process may be repeated in the future without repeating the reasoning. When, however, the formula is used without the previous thought process, as when it is copied out of a textbook, there is the danger that it will be misapplied or forgotten, and even when applied correctly the process is nearly devoid of
educational value. Instead of depending on the memory to retain several algebraic equations, we may use the kinetic theory, a very simple conception, and by the aid of easy
logic solve any problem in the gas laws, as illustrated above. The only numerical value that needs to be remembered is
that
C.
will
is
273 K.
see, however, how a general gas law may be obtained. carry out the process followed in paragraph 13, but using algebraic, general quantities instead of specific arithmetical values. Consider 1 mole of gas, grams, under standard conditions, PQ, V Q r and find what the volume of grams will be, v, at some other pressure, p, and temperature,
Let us
We
M
T.
Changing p Q to p while keeping
TQ
the same changes the
15
THE KINETIC THEORY
47
volume to Vopo/p, and then changing to T while keeping p the same changes this volume to T/T of its former value
giving VQp Q T/pTQ If, finally, we use of grams, v = wvQp Q T/MpTQ writing the more striking form,
.
w grams of gas instead We may rearrange this,
pV ~T
__ ~
W_
ppVp
'
~M
we follow the universal R, a constant, called the "gas constant/* Its numerical value depends, of course, upon the units chosen for expressing p Q V Q and TQ Using atmospheres^ and Kelvin degrees, R = 1 X 22.4/273 = 0.0821 liters, (cf. Chapter IV for the value of VQ.) Using cm. of mercury and cc., R = 76 X 22,400/273 = 6240. The general gas equation can then be written
VQ,
Now pv,
and
TQ
are fixed values, so
practice of setting pQV Q /T
(1)
for
grams
of gas or
pv
= RT
(2)
for 1 mole of any gas. We may solve these equations for any one of the quantities which may be unknown in a particular
We must be careful, however, to express R in the units used for p, v, and T. Suppose, for example, we wish to calculate the weight of oxygen, in grams which will exert a pressure of 100 mm. of mercury at 27 C. in a vessel having a capacity of 600 cc. If we happen to remember R only in liter-atmospheres, 0.0821, then we must express p in atmospheres, y$$
case.
>
and
M = 32.0 grams. Accordingly,

pvM = = 15.
v in liters, 0.600,
and since we want
w
=
in
grams we write
100
760
X X
0.600
0.0821
X X
32.0
300
somewhat oversimplified derivation of the p, number of molecules, n, mass per molecule (molecular weight), m, volume, v, and average molecular
following
relation
The
between pressure,
48
velocity, w,
may
prove helpful to some. Imagine a cubic box,
side; a single molecule
Ch.
Ill
cm.
on a
posite walls with velocity
moving back and forth between opx would hit x/l times per second, with
an impulse of 2 mx (the change of momentum) at each impact. The 2 force on these walls is thus 2 mx /l. The velocity in the jc-direction
is
u
2
J-
12
only one component of total velocity, u, the relation being = xz + y2 + 22 where y and z are the other components of
,
velocity.
2
2
The
total force exerted
by
molecule on
all six
walls
is is
ww //, and the ww //3 since the
corresponding pressure (force per area), p, area is 6 / 2 The volume of the box is v = / 3 so
. ,
that the pressure for n molecules
is
p =
nmu*/v
(3)
Now, $ mu* is the average kinetic energy per molecule, which is, by the theory, assumed proportional to the temperature, provided
that temperature is reckoned, not from C., but from the point where molecular velocity ceases, the real "absolute zero." Writing
mu* = kT, where T is the temperature on the new scale and k the universal "Boltzmann constant" of proportionality, we have,
\
pv
It is evident that
= nkT
(4)
in equation (2). nk in equation 4 is identical with In the derivation given above it has been assumed that all the molecules have the same velocity. Actually, of course, this cannot
be true, for a molecule may move after a collision either faster or slower than before. The distribution of velocities and its change with temperature are shown in Fig. 2, p. 173.
16. In drawing the various conclusions given above concerning the relations between pressure, volume, amount and temperature, we must remember that we have assumed that when the gases are
sufficiently
expanded the volume occupied by the molecules them-
selves
negligible compared with the volume of the vessel, also that they are so far apart and moving with such high velocity that
is
mutual attractions can be neglected. The higher the temperature and the lower the concentration, the more nearly do these assumptions correspond to the truth. On the other hand, as the
their
temperature
is
lowered and as the concentration
is
increased,
in-
creasing deviations are to be expected from the behavior previously deduced, becoming more and more marked until the attractive
forces
become
sufficient to cause the molecules to
condense to
*che
17
liquid state.
THE KINETIC THEORY

The
49
conditions under which this condensation takes
place obviously depend upon the kind of molecules involved. With the gas helium, at a pressure of one atmosphere, the temperature must be lowered to 4.5 before liquifaction takes place.
The deviations actually found from the ideal gas laws are illustrated in Fig. 6 for H2, C>2, and CO2, where the experimental values of pv are plotted against p. The quantity of gas and the units used
have been arbitrarily selected so as to make pv
1,5
at low pressures.
H2
1.0
0.5
pv
100
200
Deviations from Boyle's Law.
300
P
Fig. 6.
In the case of hydrogen, pv increases right from the start. This can be explained as due to the fact that molecules themselves take up part of the space of the container, which is v, causing the molecules to strike the walls more frequently than they otherwise would, and also to the weakness of the attractive forces between hydrogen
molecules, as could be inferred from the very low temperature
necessary to liquefy it. Oxygen molecules attract each other more strongly, making p smaller at first, and CO2 molecules attract each
other
in
still more strongly, causing pv to dip to 0.5 at 100 atmospheres; other words, the actual volume of the gas at this pressure would be only 0.5 of what it would be if CO 2 were an ideal gas.
,
17. van der Waals' Equation. The Dutch physicist, van der Waals, designated the actual volume of the molecules in 1 mole of b, and he gas as b, so that the free space in the vessel becomes v the attraction between the molecules as a/v z where a expressed is another constant. Since the pressure of a real gas is made smaller than the pressure of an ideal gas by reason of this attraction, we
,
50
correct
Ch.
119
it by adding a/v*. The ideal gas equation, equation transformed in this manner into
(2), is
)(
6)
= RT.
(5)
This agrees much better with the behavior of highly compressed gases than does the simple pv = RT, and values for a and b can be chosen which will permit the van der Waals' equation to agree approximately with the actual values such as those in Fig. 5. The agreement is far from perfect, however, so^that the equation is to be regarded only as the next approximation. The progress of science seldom consists in reaching absolute truth but in closer and
closer approximation to
it.
18. Partial
Pressure of Different Gases in Mixtures. The
kinetic theory also enables us to predict correctly certain properties of gaseous mixtures. In the first place, we would expect the gas laws to hold for mixtures of gases as well as
for pure gases, as is indeed the case. In the second place,
we
would expect the molecules of one species to maintain the same average kinetic energy at the same temperature regardless of the presence of any other species of molecules, and therefore the part of the pressure which is due to the impacts on the vessel walls of one species, called the partial pressure of that gas, would be the same no matter what other gases are present. This law is usually known as Dalton's Law. By way of illustration, let us suppose a closed vessel containing water and carbon dioxide gas maintained at a constant
temperature. Some of the carbon dioxide will dissolve in the water. Suppose now that some other gas, say nitrogen, is
amount
would this affect the injected into the same vessel. of carbon dioxide dissolved in the water? Without
How
the aid of the kinetic theory one might suppose that more carbon dioxide would be forced into the water, but from the molecular-kinetic standpoint we see that the number and
momentum of the carbon dioxide molecules striking the water surface, upon which alone the solubility of the gas
depends, are practically unaltered by the presence of the nitrogen molecules.
18
THE KINETIC THEORY
51
The form in which Dalton announced the law known by his name was not identical with the statement here given. His studies
antedated the kinetic theory, a fact which makes this and other discoveries of his the more remarkable. In one place 1 he says, ". the elastic or repulsive power of each particle is confined to those of his own kind; and consequently the force of such a
. .
fluid, retained in a given vessel, or gravitating, is the same in a separate as in a mixed state, depending on its proper density and temperature." With reference to the solubility of a single constituent
of a mixture of gases he said, "If a quantity of water free from air be agitated with a mixture of two or more gases (such as atmospheric air) the water will absorb portions of each gas the same as if they
were presented to
it
separately in their proper density."
Again, suppose we consider two vessels of equal size, one evacuated and the other containing oxygen, both kept at the same temperature. If water is introduced into the first one, a little of it will vaporize, since the molecules of the liquid are in rapid motion with a velocity depending on the temperature, and certain molecules at the surface which have unusually high velocities may be able to escape the attraction of the liquid and go into the vapor phase. As the
number of molecules in the vapor phase increases, there is a constantly increasing chance that some of them, moving more slowly than usual, will be caught into the liquid again, instead of rebounding at the surface. The concentration of molecules in the vapor state thus tends to become adjusted,
is an equilibrium or balance between the two phases such that the number of molecules of liquid vaporizing in a given time just equals the number of molecules of water condensing in the same time. The pressure of vapor necessary for this equilibrium depends on the nature of the liquid and on the temperature, increasing as indicated by the curves
so that there
Alembic Club Reprints, "Foundations of the Atomic Theory," No. 2, p. 1, by William F. Clay, Edinburgh, 1893. This reprint, together with No. 4, which quotes brief papers by Dalton, Wollaston, Thomson, Gay-Lussac, and Avogadro, gives the steps, experimental and logical, by which the conclusions presented in Chapters I to IV in this book were reached. It might comfort a
1
published
reader
who
finds these matters a bit difficult to learn that the able
men who
worked them out did not
find
them
easy.
Ch.
Ill
in Fig. 7. It is obvious that this pressure will not depend on the extent of the liquid surface, as an increase in surface has the same effect on the number of molecules vaporizing as it has on the number condensing, so that the net effect is zero.
Suppose, now, we admit water to the second vessel, containing oxygen. Evidently the tendency of molecules of
1500
11000
760
500
/w
40
60
80 Temperature,C
of
liquids.
100
Fig. 7.
Vapor pressure and temperature
A, ethyl alcohol;
chloroform; E, ethyl ether;
W,
water.
liquid to escape will be the same as before, but the vaporized molecules will be unable to distribute themselves so rapidly
throughout the vessel, since they must diffuse through oxygen molecules which collide with them and retard their progress. Hence the liquid will evaporate more slowly than in the previous case, where oxygen was absent, but eventually the molecules of water vapor will be distributed throughout the vessel just as if the oxygen were absent, and the partial pressure of the water vapor will be independent of the other
gas (or gases) present. 19. Relation between the Pressure of a
Gas and
Its
Solubility in a Liquid. When a gas is placed over the surface of a liquid, it dissolves to an extent dependent on the nature
20
THE KINETIC THEORY
53
of the gas, the nature of the liquid, the temperature and the pressure of the gas. When no more gas will dissolve in the liquid, we have a state of equilibrium, in which the
number
of molecules of gas being

is
caught into the liquid

is
in
given time
number escaping. Suppose, now, that more of the same gas

the same as the
introduced
into the space above the liquid. If the temperature is kept the same, the momentum of the molecules striking the surface
of the liquid is unaltered, but the number so striking is increased, so that more of them enter the liquid than escape
from
it,
and the added number of dissolved molecules
finally
again equals the number entering. An increase, therefore, in the pressure of the gas above the liquid causes an increase in the amount of gas dissolved by it. We would naturally expect this amount dissolved to be proportional to the pressure, which is apit
increases the
number escaping
until
proximately true for gases which are not too soluble and do not react chemically with the solvent. This is known as
Henry's Law. 20. Avogadro's Rule. One more consequence of the kinetic theory should be given at this time, as it will play a very important part in the reasoning in Chapter IV. When two different gases are at the same temperature,
the average kinetic energy of the two different kinds of molecules is the same. We conclude that this is true from
the fact that when two different gases at the same temperature are mixed the total resulting pressure is the sum of the partial pressures each gas would have if the other were
absent; hence the kinetic energy of neither is altered by the mixing, which can be the case only when they have the same
of equal volume, such
kinetic energy before mixing. Let us then take, in two vessels amounts of two different gases at the
their pressures will be the same. have seen that the pressure of a gas depends upon the number of molecules, their kinetic energy, and the volume they occupy, and upon no other factors. Since, therefore, we have chosen equal pressures, volumes, and temperatures
same temperature that
Now we
54
Ch.
Ill
(and hence kinetic energies) the only other factor, the number of molecules in the two quantities of gas, must likewise be the same. In other words, equal volumes of all gases, at the
same temperature and pressure, contain the same number of molecules. This was first announced by an Italian physicist,
Avogadro, in 1811, and is usually called Avogadro's Rule or Law. We will use it presently to measure the relative numbers
of molecules involved in chemical reactions.
drawn can be more concisely expressed aid of the equation, pv = nkT, derived in paragraph 15. Letting the subscripts 1 and 2 stand for two different gases, we write p&i = n^kTi and p z v 2 = n 2 kT 2 Let us take two vessels of equal size, so that vi = z> 2 and hold them at the same
21.
The
conclusion just
in algebraic terms,
by
temperature, so that Ti = T 2 and adjust the quantities of the two gases so that pi = 2 then it follows that n\ = n 2
,
Effect on temperature of a gas of a, Fig. 8. compression; b, expansion while doing work; <:, expansion of a dilute gas into a vacuum; d, expansion of a compressed gas into a vacuum.
22. Other consequences of the kinetic theory may readily be drawn. For example, the molecules of a gas striking a compressing piston rebound with increased velocity just as is the case with a baseball struck by a batter; hence they are hotter and the
process
cooled,
on a retreating piston is This occurs both in steam engines and gasoline motors. On the other hand a molecule leaking through a fine hole into
cf. Fig. 86.
,
of compressing heats the gas, cf. Fig. &a. true, and a gas expanding by doing work
The
reverse
is
of course
24
THE KINETIC THEORY
55
a vacuum is not cooled, any more than a ball is retarded by passing through an open window, cf. Fig. Sc. However, if the gas is highly compressed, then, on expansion through an orifice the mutual attractions of its molecules may be enough to cause retardation as they move apart, just as a ball is retarded when rising against the
earth's gravitational attraction, the liquefaction of air. The air
cf.
is
Fig. Sd. This effect
is
used in
highly compressed, cleaned of moisture and carbon dioxide, cooled to remove the heat 6f comliquid
itself.
pression, first by water, then, in certain plants at least, by ammonia, then by air that has already expanded and cooled
Part of this strongly cooled air then liquefies on expansion through
an
orifice.
different gases
Molecular Velocities and Diffusion. Since the molecules of have equal translational energies at the same tem= \ W 2 w 2 2 (cf. paragraph 15) where perature, we can write | m\u^
23.
the subscripts refer to the two species, whence UI/HZ = ^/m^/m\. for which mi = 2, and the second If the first gas is hydrogen, 2
which ra 2 = 32, then u\ = 4 u^ that is, hydrogen oxygen, molecules move on the average four times as fast as oxygen molecules at the same temperature. We may conclude from this that
is
2,
for
hydrogen could diffuse through a small hole or down through another gas four times as fast as oxygen. The actual mean velocities can be calculated from equation 3. We will obtain u in centimeters per second if we use the molal
gas
M, in grams, and p in dynes. Let us take 1 mole of weight, nm C. and 1 atm., then, since 1 atm. = 76 cm. in 22,400 cc. at = 76 X 13.6 grams = 76 X 13.6 X 980 dynes = 1.013 of Hg 10 6 dynes, we obtain
[sj^ V~TT =
2.6
r=~" cm ./sec.
10 5
5 giving u = 1.85 X 10 cm. /sec. or 1.85 kilometers per second (1.15 miles per second). The corresponding figure = 32, is 0.46 km. /sec. or 0.29 mile/sec. for oxygen, where
for
hydrogen
is 2,
of Gases. If a monatomic gas, such as heliui; He, neon, Ne, argon, A, or mercury vapor, Hg, is heated in a of fixed volume, all of the energy absorbed goes into the kinetic energy of the molecules. We can calculate tj;
24.
Heat Capacity
aid of equation 3, 3 pv
= nmu 2 The mean

.
kinetic
56
molecules
is
\
Ch.
Ill
this is equal (paragraph 14) to one degree higher, T 1, the kinetic f RT. At a temperature energy is greater by an amount equal to f R. It is convenient for this purpose to take the value of R not in liter-atmospheres per degree per mole, as in paragraph 14, but in calories per degree per mole, 1.987. The heat required to raise the temperature of 1 mole
mmi 2 = f pv, and
monatomic gas 1 C. is f X 1.987 or 2.98 calories when the volume is kept constant. This heat capacity is usually designated
of
If the pressure is kept the same during the heating, work has to be done against the external pressure and a larger amount of heat
GB
Fig. 9.
molecule;
Internal energies of molecules, o, rotation; 6, vibration of diatomic c, d, e, modes of vibration of linear triatomic molecule, e.g., OCO.
is
RT
1
is
f = equal to the pressure times the increase in volume, p(v v) = R = 1.987 cals. The heat capacity at constant R(T 1) pressure, designated Cp exceeds C v by R calories per degree, i.e., Cp - Cv = R.
required to raise the temperature of the gas 1 C. Writing pv = and pv' = R(T 1) for the gas before and after heating C., respectively, the work done against the external pressure
RT
On heating a gas whose molecules contain more than one atom, the kinetic energy is increased by f -R, as with monatomic molecules, but additional energy can be absorbed by rotations and
will
internal vibrations of the molecules, as illustrated in Fig. 9. These vary in magnitude depending on the constitution of the mole-
cules.
Of course Cp
Cv =
R,
as with
Table 2 gives
illustrative values for gases
monatomic molecules. whose molecules have
varying .complexity.
25
THE KINETIC THEORY

TABLE
2
57
Approximate Values
for
Heat Capacities
at
5C
The
ratios,
CP /CVJ
from the velocity of sound

25. Solids
given in the bottom row, have been calculated in the gas, which depends on this ratio.
of a gas is lowered, the kinetic energy of the molecules decreases until a point is reached where the attractive force between the
in the van der Waals equation, equation 5, with the external pressure, causes the molecules together to condense to liquid. The higher the external pressure the higher the temperature at which condensation can occur. Our picture of a liquid is one in which the molecules are in vigorous motion, with sufficient space in which to change their positions continually, but without sufficient kinetic energy to enable any but the fastest among them to escape into a vapor space above the liquid. Molecules in the vapor phase close to the liquid surface which happen to be moving slowly as a result of the most recent collision may be caught into the liquid. A liquid and its vapor in contact at constant temperature quickly reach a state of balance or equilibrium in which the number of molecules which escape from the liquid to the vapor in any interval of time is the same as the number of those which reenter the liquid, and their concentration or pressure in the vapor phase has a fixed value, called the vapor pressure at that temperature. Lowering the temperature diminishes the vapor pressure because it decreases the speed of the molecules, allowing them to be more easily captured by the liquid, and also because it allows the liquid molecules to crowd more closely together so that they escape
and Liquids. As the temperature
molecules, a/v
the vapor. (Intermolecular attraction often varies inversely with the seventh power of the distance.) lower pressure then suffices to restore the equilibrium;
less easily into
58
Ch.
Ill
Figure 7 shows the form of vapor pressure curves for several familiar substances, ether, chloroform, alcohol, and water. These and all other vapor pressure curves can be expressed
with
little
error
by the Clausius-Clapeyron equation,
vapor pressure, L the heat absorbed mole of the liquid, T the absolute temperature, and C a constant chosen to fit the data. This equation suggests plotting log p against 1/T, which gives a straight line which most vapor pressures fit with close approx-
where p stands
for the
in the vaporization of
'Got
2000
imation.
lowering the temperature of a liquid, the thermal

Vaporization
On
1500
agitation of the molecules diminishes, the liquid contracts,
the
1000
'liquid
fFusion
molecules
attract
each
other more strongly due to the smaller distances separating
500
I
/Solid -I
Transition
'Solid -H
them, and a point is finally reached where they can no longer wander about in the
liquid,
exchanging places, and they become fixed in a regular Heat absorbed by oxygen, array in a solid crystal lattice. Fig. 10. starting at absolute zero. showg the F j g> ^ p in crystals of a number of metals, includrangement of atoms ing aluminum, nickel, lead, copper, and silver. This is known as
50
100
150K
the face-centered cubic lattice. Here they are still free to oscillate in their places, or "cages," but only occasionally, if at all, can a pair exchange places. Melting is the reverse of this process. Many solids show one or more further transitions &s the
further lowered. Changes in the amount of vibrations within the molecule, changes in its rotation, etc.,
temperature
is
can favor one type of crystal
lattice
over another. Iron
is
**25
THE KINETIC THEORY
59
stable at high temperatures in the face-centered cubic struc-
but below about 900 C. it changes to the body-centered cubic lattice 1 shown in Fig. 4, p. 415. These changes all involve the addition or subtraction of heat and in Fig. 10 is shown the amount of heat that must
ture,
it
be added to a mole of oxygen starting at absolute zero to bring to its stable form at any particular temperature.
Exercises
See Appendix
It is
II for
answers.
recommended that the student remember that the purpose
is not simply to get the correct answers, which might be achieved simply by substituting unintelligently in the formulas found in a high school text, but rather to stimulate the exercise of the imagination. Exercises 18 and 19 are particularly
of the following exercises
good
1.
tests of this ability.
properties serve to distinguish solids, liquids, and State the distinctions in terms of the kinetic theory. gases?
2. If
What
what pressure
unchanged?
3. If
a certain quantity of gas occupies 100 cc. at 3 atm., at will it occupy 60 cc. if the temperature remains
16 g. of oxygen
size at
a certain
4.
C.,
inflate it to the
same
required to inflate a rubber balloon to of oxygen must be used to size at 20 C.?

is
what weight
To what
gas occupies 100 cc. at 127 C. and SO cm. pressure. temperature would it have to be cooled in order that a simultaneous decrease in volume to 60 cc. would produce no change
in pressure?
If an automobile tire is inflated to a pressure of 30 Ib. per gauge pressure at 15 C., what will the gauge pressure become the tire is heated to 50 by running?
Some
5.
sq. in.
if
proportion by weight of the air in an automobile tire to escape in order to reduce its gauge pressure from 35 Ib. to 30 Ib. per sq. in., the temperature remaining the same? 7. A quantity of gas occupies a volume of 40 cc. at 127 C. At what temperature will its volume become 22 cc., the pressure remaining the same?
6.
What
must be allowed
1 See Latimer and Hildebrand, Reference Book of Inorganic Chemistry Appendix V, for types of crystal lattice.
60
8.
At what temperature
1
Ch.
Ill
dioxide gas at
9.
atm.
if it
will a flask contain 3.30 g. of carbon contains 2.00 g. at 57 C. and 1 atm.?
To what temperature must an open

fifth of
flask
that one
the gas which
it
contains at 7
be heated in order C. shall escape?
10. If a balloon has a capacity of 480 cubic meters, how many tanks of hydrogen must be used so fill it if each tank has a volume of 0.300 cubic meters and contains hydrogen at a pressure of 40
atm.?
11. If 1 liter of a certain gas, measured at 76 cm. and C., weighs 1.25 g., what would be the weight of 1 liter of the same gas at 60 cm. and 47 C.? 12. A tank contains ISO g. of hydrogen at IS atm. and 17 C. What weight of hydrogen would escape if the tank were heated to 100 C. and the cock opened? 13. If the
liter
is
at
concentration of chlorine gas in a flask is 3.16 g. per C. and 1 atm., what will it be at 47 C., if the pressure
0.8 atm.?
14. A flask contained enough oxygen molecules to exert a pressure of 0.5 atm. upon the walls. If twice as many nitrogen molecules and three times as many helium molecules are introduced, what will be the pressure upon the walls?
15. If water is introduced into an evacuated vessel at 20 C. the pressure inside the vessel becomes 17 mm. of mercury. If some air which has been standing over water at 20 C. is put into a flask to a pressure of 756 mm., a piece of quicklime introduced and the flask closed, what will the pressure become when the quicklime has absorbed all of the water vapor from the air?
16.
of a gas be affected
17.
pump
18.
According to the kinetic theory how will the temperature by expansion into a vacuum? Explain briefly. in terms of the kinetic theory, why an automobile Explain, gets hot while pumping air into a tire.
of the following changes
State the effect, quantitatively where you can, of each upon (a) the number of molecular impacts second per square centimeter upon the containing walls and per (b) the force of each impact. (1) Gas in a cylinder with a movable piston, immersed in a
large water bath,
(2)
is
The
air pressure in
is
expanded from 2 liters to 3 liters. an automobile tire is slowly pumped up

in
Ib. per sq. in. to 30 Ib. per sq. in. a closed vessel at constant temperature
from a gauge pressure of 20

(3)
H2S gas
kept
THE KINETIC THEORY

19.
1
61
Consider the following quantities for two gases, designated 2, respectively: pressure, /?; volume, z>; temperature, T\ molecular weight, m\ mean molecular speed, s; number of molecules, n. If you are given the following relations between certain of these pairs of variables, you can draw conclusions regarding others. Indicate this conclusion in each of the following cases by writing in the sign, > when the first is greater than the second (e.g., pi > p* means pi is greater than 2 ), the sign, < when it is less, and the = when it is equal to the second. If no conclusions can be sign, drawn, write a question mark (?).
and
Conclusions from the Kinetic Theory. Indicate by writing in the appropriate sign,
>, <,
(a)
(b)
(c)
or?
$2
mi mi
pi HI
(d)
(e)
> w equal p, v, T\ > W2, equal p, v, T; > pi, mi > m equal > n equal p, v;
2, z, 2,
Si
n\
w2
2
T, n\
vi
TI
pi
T2
/> 2 .
Equal
v,
n, s;
*20. Divers can operate at greater depths if they breathe an atmosphere of helium and oxygen instead of compressed air because
helium is less soluble than nitrogen in the body fluids, and therefore has less tendency to form bubbles when the diver comes to the surface, releasing the pressure. This "effervescence" produces the serious and painful "caisson disease," or "bends." It is much harder, however, to keep warm in this helium atmosphere, and electrically heated clothing has been found necessary. Explain.
*21. Which gas, in each of the following pairs, would you expect or CC>2 to conduct heat faster from a hot body: (a) 2 or 2 (&) molecular weights), (c) dry air or water vapor at the (nearly equal
same pressure?
22. What difference would you infer from the kinetic theory between (a) He and Ne, and (&) Ne and O 2 in the amounts of heat energy necessary to raise the temperature of 1 mole of the gas 1 C.? *23. Helium atoms have an average speed of 1150 meters per second. The "mean free path" (i.e., average distance between 6 collisions) is 25 X 10~ cm. How many collisions does a helium
,
atom undergo per second? *24. Compare the rise in temperature for (a) A and Ne and is suddenly diminished (b) A and CO 2 when the volume of each
*
Questions of greater
difficulty,
that should not be attacked until the others
have been mastered.
to one half its former value; the initial pressures
Ch.
Ill
and temperatures
measure low
being the same.

*25.
MacLeod gauge, shown
in Fig. 11, is used to

is
pressures. A represents the vessel containing the gas at low pressure.
When
the mercury in the reservoir, C,
forced upwards
by pressure
Fig. 11.
MacLeod gauge.
previously at
in
C into
the capillary
D to a height, A", the gas in JB,
same pressure as the gas in A, is trapped and forced into the capillary* E> the mercury rising to a height, h. If the volume of B is 200 cc., and the diameter of the capillary is 0.8 mm., h' h = 100 mm., and h" h = 125 mm. What is the pressure of the
the
gas in
A?
CHAPTER
IV
MOLECULAR WEIGHTS
Fixing Formulas and Atomic Weights. In the preceding chapters a number of molecular formulas have been used
1.
without explaining how we know them to be the correct ones. The law of simple multiple proportions considered by itself merely allows us to say, for example, that if the formula of water is H 2 O, as stated in Chapter II, paragraph 6, then that of hydrogen peroxide could be H 2 O 2 or HO, since the
ratio of the weights of
7.94 in the former

of oxygen, 16.00,
oxygen to hydrogen is, by analysis, and 15.88 in the latter. These formulas
are consistent with the accepted values of the atomic weights and hydrogen, 1.008, since
16.00 Wt. of oxygen = = 2 X 1.008 Wt. of hydrogen
'
'
and
is
X X
16.00
1.008
15.88 in
H 2 O2
But the formula of water was long considered by many, among them Dalton himself, to be HO, which would be consistent
with the analytical weight ratio of 7.94 if the atomic weight of oxygen were set at 8.00. Hydrogen peroxide would then have to be 2 or some multiple thereof, to agree with the
HO
analytical weight ratio of 15.88.
How
do we now know that
water
is
HO
2
and not
HO?
The decision resulted, historically, from the discovery that molecules of elements are not identical with their atoms. Dalton had spoken, in 1808, of "an atom of water or steam, composed of
1
of oxygen
and
of hydrogen, retained in contact
by a strong
63
64
affinity,
and supposed
to be surrounded
Ch.
IV
of heat; its relative weight
8." Gay-Lussac, later in the same year, announced the law now called by his name. It is interesting to read this in his own words. "Thus it appears evident to me that
by a common atmosphere
gases always combine in the simplest proportions when they act on one another; and we have seen in reality in all the preceding examples that the ratio of combination is 1 to 1, 1 to 2, or 1 to 3.
very important to observe that in considering weights there no simple and finite relation between the elements of any one compound; it is only when there is a second compound between
It is
is
the same elements that the new proportion of the element that has been added is a multiple of the first quantity. Gases, on the contrary, in whatever proportions they may combine, always give rise to compounds whose elements by volume are multiples of each
other.
do gases combine in ,very simple proporjust seen, but the apparent contraction of volume which they experience on combination has also a simple relation to the volume of the gases, or at least to that of one of them.
only, however,
tions, as
"Not
we have
We must understand, of course, that these volumes are all measured at the same pressure and temperature. Avogadro, in 1811, seized upon this discovery to draw the conclusion now known as Avogadro 's Law, which we saw in Chapter III, paragraph 15, to be also a direct consequence of the kinetic theory. He wrote, "It must then be admitted that very simple relations also exist between the volumes of gaseous substances and the numbers of simple or compound molecules which form them. The first hypothesis to present itself in this connection, and apparently even the only
admissible one, is the supposition that the number of integral molecules in any gas is always the same for equal volumes, or always proportional to the volumes." Avogadro proceeded to explain
how
this principle, applied to the volumes of gases taking part in reactions, leads to a consistent set of formulas and atomic weights,
His work of clarification was not generally understood or appreciated, unfortunately, and the formula of water continued to be written H 2O by some chemists and HO by others until Cannizzaro revived it in 1858. Let us state the case in the language of today.
hydrogen and oxygen are made to combine at a temperature and pressure at which the resulting water is
2. If
MOLECULAR WEIGHTS
65
steam, the volumes involved are in the proportion indicated below.
Hydrogen
Relative volumes
212
+
Oxygen
, ,
> Steam
It follows from Avogadro's Law that the molecules are involved in the reaction in the same proportion. Let us note particularly that 1 volume of oxygen suffices to produce 2
volumes of steam and therefore that 1 molecule of oxygen has enough atoms in it, at least two, to give 2 molecules of steam. Its formula must be O 2 or O 4 etc. But no reactions are known in which 1 molecule of oxygen gives more than 2 molecules of another compound containing oxygen, hence
the formula,
O2
explains
all
the
known
facts.
volumes of hydrogen and steam in the above reaction tells us only that the number of hydrogen atoms in both molecules is the same. It could be one atom
ratio of the
The
per molecule so far as this particular reaction is concerned; however, there are many other reactions known in which 1 molecule of hydrogen gives 2 molecules of some other gas;
never more. Such a reaction
is
Hydrogen
Relative
volumes
11
and
Chlorine
>
Hydrogen
2
chloride
The molecule
of hydrogen, therefore,
its
cule of chlorine, from this
must be 2 other reactions,

is
The moleis
C1 2
We now possess other criteria for distinguishing monatomic

and polyatomic molecules. One
of these
furnished
different heat capacities of gas molecules of differing plexity, as set forth briefly in Chapter III, Table 2.
3.
If this
by the comit
reasoning seems at
all
puzzling
it is
because
to carry out a logical process in unfamiliar terms, where one's imagination cannot serve as a prop. problem involving the price of bandersnatches in rupees would bother
is difficult
could solve the same, problem on the price of sheep in dollars. The difficulty is one that can be minimized
persons
who
66
training,
Ch. IV
by
one's education.
and such training is an important element in The aim should be to learn to reason just " " as confidently and correctly with unknowns, such as x and y, as with familiar terms such as apples and boys. Let us
illustrate the simple
nature of the argument in the preceding
paragraph by using familiar units. Suppose you were told that an unknown number of apples had been divided equally among a certain number of baskets, and, further, that the apples in these baskets had later been divided equally, without cutting any apples, among twice
as many boys as baskets. What conclusion could you draw about the number of apples in each basket? You would doubtless have little hesitation in stating your conclusion
somewhat as
baskets, twice as
tain
in
all
follows: If the apples in a certain

filled
number
of
many
alike, can be distributed evenly among boys as baskets, then each basket must con-
an even number of apples, at least two. The reasoning paragraph 2 is no more difficult than this. It is, simply: If the atoms in a certain number of molecules of oxygen (all alike, since it is pure substance) can be distributed evenly
among
twice as
many
molecules of water, then each molecule

least
of oxygen
must contain an even number of atoms, at
two. It sometimes pays to substitute familiar for unfamiliar terms just to overcome one's inhibitions. have seen that the molecules 4. Molecules of Elements.
We
of hydrogen, oxygen, and chlorine each contain two atoms. The same is true for nitrogen, fluorine, bromine, and iodine.
Another variety of oxygen exists, called ozone, formed from oxygen by the silent electric discharge, with a diminution in volume in the ratio of 3 to 2, indicating that the equation must be written
3
O2 =
O3
The molecule of ozone, therefore, contains three oxygen atoms. The molecule of phosphorus vapor at low temperatures is ?4, at higher temperature P%, that of sulfur may be S8 82, or S, according to the temperature. When metals are
,
'MOLECULAR WEIGHTS
67
vaporized their molecules nearly always consist cf single atoms. The same is true of argon, neon, and helium, gases existing in small amounts in the atomsphere. 5. Changes in Volume or Pressure in Gas Reactions.
The connection we have

cules
traced between the volumes of
gases in chemical reactions and the relative number of molemay be used conversely to deduce the change of volume
or pressure to be expected when reactions take place between substances whose formulas are known. Consider, for example,
the reaction represented by the equation

2
SO2
+ O2 =
SO3
If this reaction is carried
out at a temperature at which
all
of the substances represented are gaseous, then we see that three molecules have formed two. If the temperature and
volume have been kept the same during the reaction, this will result in a decrease of the pressure to two thirds of its former value. If the temperature and pressure are the same as before, then the volume will be two thirds of its former
value.
be used to deduce relative volumes, tc use the correct formulas of the substances in the gaseous form. For example, the same weight, 28 g., is indicated both by N 2 and 2N, but the second formula is incorrect, and would lead us to expect twice the volume which would actually be involved. 6. Volume of One Mole of Any Gas. The double meaning attached to chemical symbols and formulas was explained in Chapter II, one referring to single atoms and molecules, and furnishing a basis for reasoning, and the other referring
It is important,
will
whenever an equation
to the gram-atom and gram-molecule, or mole, and furnishing a basis for experimental work. Having determined that equal numbers of gaseous molecules are contained in equal
volumes, at equal temperatures and pressures, and that the mole of all substances consists of the same number of molecules, it becomes important to ask what is the actual volume occupied by the mole of gas. This rests upon
68
Ch. IV
the measurement of gas densities, as illustrated
by the
Vol. of 1
C., 1
fol-
lowing table:
Wt. of 1
liter
Gas
C.,
1 atm.
g.
Vol. of 1 g. C., 1 atm.
g.
per
mole
aim.
mole
2.016 32.00 28.02
17.03
H2
O2
0.08988
11.126
1.
1.
1.
22.431.
N2
NH*
1.4291 g. 1.2507 g.
0.0998 0.7995
22.39 22.40
1.
1.
0.7621
g.
1.31221.
22.351.
mole of gas under standard conditions, as well as others that might be added, are all very close to 22.4 liters, which may therefore be selected as the molal volume of a gas under standard conditions. (This is the volume of a cube 28.2 cm. or 11^ inches on the side.) We may take this volume as the basis of our
These values
for the
volume
of the
working definition of molecular weight, saying that the molecular weight of a substance is the number of grams of it which occupy 22.4 liters when it is in the gaseous form and under standard conditions. Very frequently, of course, substances cannot exist in the vapor state under these conditions, so that the relation between the weight and the volume of vapor must be found experimentally at some higher temperature, and perhaps lower pressure, after which it is possible
to calculate the weight that 22.4 liters of the vapor would C. and 1 atmosphere, if no condensation took have at
place.
7.
We may
it is
illustrate
by examples the various types
of
problems
ship.
possible to solve with the aid of this relation-
Given Volume or the Volume of a Given Weight of a Gas. Example: What is the volume of 10 g. of O 2 at 127 C. and 0.5 atmosphere? The answer to
Calculation of the
Weight
of a
this
is
obtained by the following obvious steps:

2
occupy 22.4 1. at 273 K. and 1 atm. g. of O2 occupy 44.8 1. at 273 K. and 0.5 atm. g. of O2 occupy Qft X 44.8 1. at 400 K. (127 C.) and 0.5 atm.
32 32 32
g. of
9
1
MOLECULAR WEIGHTS
g. of
69 at 400 K. and
at 400
O2
2
occupies
^ X &ft X 44.8
1.
1.
0.5 atm.
10 g. of
occupy
M X $n X 44.8
or 20.5
1.
K.
and
0.5 atm.
Example: What is the weight of 50 1. of CO2 measured at 25 C. and 3 atm.? At 273 K. and 1 atm. 22.4 1. of CO 2 weigh 44 g. At 273 K. and 3 atm. i X 22.4 1. of CO 2 weigh 44 g. At 298 K. (25 C.) and 3 atm. ff| X i X 22.4 1., or 8.16 1., of CO 2 weigh 44 g. At 298 K. and 3 atm. 1 1. of CO 2 weighs g^fe" g. At 298 K. and 3 atm. 50 1. of CO 2 weigh 50 X -Q*T& g-> or 270 g.
Determination of the Relative Weights of a Gas and important to know whether a gas is heavier or lighter than air. The proportion of nitrogen to oxygen in air is very nearly 4 to 1 by volume, so that in 22.4 liters of air four fifths of the molecules would be nitrogen and one fifth would be oxygen. Taking four fifths of 22.4 liters of nitrogen under standard conditions, weighing four fifths of 28.0 g., and mixing it with one fifth of 22.4 liters of oxygen, weighing one fifth of 32.0 g., we would get 22.4 liters of air weighing 28.8 g., under standard conditions. Suppose we wish to know the relative density of the following gases with 3 HC1, C1 2 We can find their molecrespect to air: C0 2 ular weights with the aid of the atomic weight table, and conclude that 22.4 liters under standard conditions would 17 g.; HC1, have the following weights: CO 2 44 g.; 3 36.5 g. C1 2 70 g. air, 28.8 g. This shows at once the relative weight of each with respect to the air. 9. Determination of Molecular Weight. Example: What is the molecular weight of phosphorus vapor and what is its formula, given the atomic weight, P = 31.0, and the experimental determination that a flask having a volume of 583 cc. was filled with the vapor at 310 C. and a pressure of 756 mm., and that it was found on cooling to captain
8.
Air. It is often
NH
NH
70
Ch.
IV
the
1.49 g. of phosphorus? The molecular weight is found from number of grams occupying 22.4 liters at 273 K. and
760 mm., which must therefore be calculated.

Since 1.49
g.
of phosphorus
vapor occupied 583
cc. at
756 583
mm. and
583 K.,
1.49 g. of phosphorus vapor would cc. at 760 mm. and 583 K., 1.49 g. of phosphorus vapor would
occupy yff
occupy
fH X yf
1.
583
cc. at
760
mm. and
273 K.,
1.49 g. of phosphorus vapor at 760 mm. and 273 K.,

2 O^ 7i5 X
would occupy 0.2715
1.49 g., or 123 g., of

1.
occupy 22.4
Since 123
g.
at 760
mm. and
phosphorus vapor would 273 K.
1. under standard conditions, 123 is approximately the molecular if it did not condense, weight. Since the atomic weight is 31, there are evidently 4 atoms in the molecule, so that the formula is P 4
.
would occupy 22.4
10.
of
As another example we may determine the formula a compound, found by analysis to contain 40, per cent of
carbon, 6.67 per cent of hydrogen, and 53.33 per cent of oxygen, and of which 0.50 g. gave 328 cc. of vapor at 200 C. and 750 mm. We will first find the relative number of atoms of each element in the molecule of the compound. From the per cents given we may say that
40
/.
g.
C
"
combines with 6.67

"
" "
12 g.
"
g.
and 53.33
g.
g.
of
O
16 g.
if .X 6.67
2 g.
1
and
or
1 1
g.-atom
or
atom C
"2 H and "2 atoms H and atom

g.-atoms
1
,
if
53.33
g.-atom O.
The formula might therefore be CH 2 O. However, the same proportions by weight would be found if the formula were
C2 4O2 or C 3 6 O3 or any other multiple of 2 O. In order to distinguish between them we must therefore determine the number of grams per mole, which is numerically equal
to the molecular weight.
CH
12
MOLECULAR WEIGHTS
71
Since 0.5 g. occupies 328 cc. at 750 mm. and 473 K. X 328 cc. at 760 mm. (200 C), 0.5 g. would occupy
$n
and 473 K., and

or 187 cc. at 760
0.5 g.
mm.
would occupy and 273 K.
f-ff
H% X
328
cc.,
the weight of gas contained in 22.4 liters, or 22,400 mole, and since 187 cc. weigh 0.5 g., 1 cc. would cc., is weigh 0.00267 g. and 22,400 cc. would weigh 22,400 X 0.00267 g., or 60 g. Of the various multiples of CH 2 O the one having a molal weight of 60 g. is C 2 H 4 2 hence this is the correct formula. 11. Direct Relation between Volumes of Gases and Weights of Other Substances in Reactions. Example: When
1
;
Now
limestone
is
decomposes, as represented
heated to a sufficiently high temperature, by the following equation:
it
CaCO 3 = CaO + CO2
Suppose we wish to calculate how many liters of CO2, measured at 20 C. and 10 atmospheres pressure, should be obtained from 2 kilograms (2000 g.) of CaCO 3 It is not
.
necessary to calculate the weight of CO 2 since the equation can be interpreted so as to give directly the relation between
,
the weight of
CaCO3 and
> CO 2
the volume of
:
CO2 We may indicate

.
this relationship as follows
CaCO3
1
mole!
g.
j
100
glVeS jl
"
mole
1.
J22.4
at 273
"
1.
K. and
"
"
atm.
"
1 atm. K. and 10 atm.
.-.2000g.
4481.
"
"
"
|f |
TO
X 448 X Mf X
is
at 293
K. and
at 293
448.
1.
The
is
resulting
volume
48.1
Complete Interpretation of Chemical Equations. It possible now to summarize what has been presented in this chapter and the preceding one concerning the interpretation of chemical equations, both as to weight and volume
12.
relations, bearing in
mind that a formula
weight of substance, and, when
a certain the substance exists in the

signifies
72
state,
Ch. IV
a certain volume under standard conditions. volumes of liquids and solids can be calculated from the measured density, d grams per cc., whence 1 g. grams M/d cc. We may recall that occupies \,'d cc. and formulas are interpreted in two ways, one referring to atoms and molecules, the other to gram-atoms and gram-molecules, or moles. This double interpretation may be illustrated by using an equation as in the following table, writing under each formula its significance in both senses.
gaseous
The
niolal
C0
(1)
(gas)
+ C
(solid)
CO
(gas)
Weights oxygen atom = 16

Relative volumes
in
terms of
44
1
12
1
56
Number of molecules
atom
2 2
+ +
C
12
1
CO
(2)
(gas)
(solid)
CO
56
2
(gas)
Weight
in
grams
C.,
44
1
Number
Volume
1
of moles
g.-atom
cc.
of
^2
atm.
22.4
1.
d
6
44.8
1.
Number of molecules
^
is
102:
10 23
^^
1Q23
(atoms)
The
last
row
it
of figures
will
is
added
for the sake of interest,
not because
represent
all
that
be used in problems. The other data necessary in order to solve any problem
involving weights, or volumes of gases, provided that one knows how to apply the gas laws to get the relation between
conditions.
the volumes of gases at standard conditions and at other It must be noted that this generalization connecting weights and volumes is possible only where gases are involved. With liquids and solids the densities of the
particular substances must be determined by experiment. The great difference between the volumes of equivalent
quantities of gases, liquids, and solids should be appreciated.
13
MOLECULAR WEIGHTS
73
If the carbon in the above equation is in the form of graphite, whose density is 2.25, the volume of 12 g. of it is 5.33 cc. The relative volumes of 12 g. of graphite ami 44 g. of CO 2 in both liquid and gaseous forms are represented to scale in Fig. 1.
Grom-otom
of graphite
Mob CO 2 gai,
1
Molt
atroo*.,
0C
CO 2 liquid
34.3 atmoi.,
0C
Fig.
1.
Relative volumes.
Molecular Weights of Dissolved Substances. impossible to determine the molecular weight of a the volume of its vapor, owing to decomposition on for example, decomposes instead of vaporizing when first to caramel and then charring. Some property
13.
It is frequently substance from
heating. Sugar, heated, turning other than the
density in the vapor state is therefore necessary in order to determine its molecular weight, and to decide which multiple of its empirical formula, C^H^sOn, is the correct one. Hydrogen peroxide, likewise, is very unstable, except when in a dilute solution, decomposing often with explosive violence when in the pure state. Analysis shows that it contains twice as much oxygen in proportion to the
hydrogen as does water; hence, having decided that water is represented by the formula H 2 O, we may conclude that hydrogen peroxide must be represented by one of the formulas HO, H 2 O 2 H 3 O.3, etc. These arc alike in the proportion of hydrogen to oxygen, 1 to 16, but differ in the total weight of the molecule, i.e., the molecular
,
weight.
etc.
To
we must
find out
distinguish between these possible formulas, therefore, whether the mole weighs 17 g. or 34 g. or 51 g.,
For such substances the molecular weight must be determined under conditions such that the substance does not decompose, which is the case often in dilute solutions.
74
14.
Among
Ch.
IV
the properties of a solution which depend upon the molecular weight of the dissolved substance (called the solute) are
the vapor pressure, the boiling point, and the freezing point. To understand the nature of the effect of a solute we may apply agair
the kinetic theory. If we have a pure liquid in contact with its vapor in a closed vessel, we imagine that there is a constant inter-
change of molecules between the two phases, molecules going from the liquid into the vapor phase at the same rate that others go from the vapor phase back into the liquid. This distribution between liquid and vapor is illustrated in Fig. 2a for a pure liquid.
a vapor pressure of pure liquid, and 6, of the same liquid in which 0.2 Fig. 2. of the molecules have been replaced by molecules of a nonvolatile solute having
t
approximately the same intermolecular force of attraction.
Suppose, now, that a certain proportion of the solvent molecules, say 0.2, is replaced by molecules of some solute which is not appreciably volatile and which does not alter the attractive forces holding the molecules of solvent in the liquid phase. Since there are now only 0.8 as many molecules of solvent present in the liquid
phase as before, the number in the vapor phase and hence their pressure will be reduced to 0.8 its former value, as illustrated in Fig. 2b. Of course, if the molecules of the solute introduced exert
a stronger attraction on the solvent molecules, they will be individually less able to escape into the vapor than before, so that
their
than
case,
0.8,
number and therefore their aggregate pressure would be less and vice versa. The effect on vapor pressure in the ideal
is
where there
no alteration
in the attractive forces, is repre-
sented graphically in Fig. 3. If the solution is composed of n\ moles of solvent and 2 moles of solute (these roles are actually inter-
15
MOLECULAR WEIGHTS
+ #2)
and
their
75
changeable) then the fraction of solvent molecules in the solution
vapor pressure, p\, is the of the pure solvent, 1, or of the vapor pressure
is
n\j(n\
same
fraction
pi
Pi*
(1)
This
is
known
,
as Raoult's Law.
Evidently Raoult's
Law
can be used to determine the number
of moles, w 2 represented by a certain weight of solute in n\ moles of solvent. Suppose, for illustration, that it was found by experiment
solved
that 19.40 g. of iodine disin 38.0 g. of CS 2
1QO
lowered the vapor pressure CSz from 433 mm. at 30 C.,the value for pure CS 2 to 378 mm. for the
of the
,
80
60 40
iodine solution. Putting pi
378
and
pi
433
0.874
in
equation
n\/(n\
(1) gives
2 ).
20
+w
The molecular
76.0, there1.0
weight of
fore the
it in
is
CS 2 is
is
0.8
0.6
0.4
fraction
0.2
number of moles of
0.500,
Mole
Fig.
3.
38.0 g.
which
n\
Substituting
this solvent
when
Lowering of vapor pressure of a its mole fraction is reduced

solute
'
in the preceding equation
by adding a
Raoult
'
Law
'
= 0.0718, the number of moles of iodine gives the value of n 2 19.40 g. One mole of iodine is, accordingly, 19.40/ represented by 0.0718 = 270 g. Since the atomic weight of iodine is 127 its molecule
must be
The
I, or I 3 etc., with a molecular weight 254. between 254 and 270 must be attributed to exdiscrepancy perimental errors and to deviations of this solution from Raoult's Law.
1%,
rather than
15. Instead of measuring the number of dissolved moles by the lowering of the vapor pressure of the solvent, the temperature being kept the same, we may, on the other hand, keep the pressure
the same, say 1 atmosphere, and determine how much the temperature must be increased in order to make the vapor pressure of the
solvent great enough to continue boiling, i.e., we may measure the rise in the boiling point produced by the added solute. The
relation
between the
rise in
temperature when solute
is
added
in
76
Ch.
IV
order to continue the boiling under
1 atmosphere pressure, and the of vapor pressure when solute is added at constant temlowering perature, as shown in Fig. 2, depends on the change in vapor
pressure caused by changing the temperature. This is related to the heat of vaporization of the solvent by Equation (6), Chapter III. In the case of water, the theoretical rise in the boiling point is 0.52 C. for 1 mole of solute in 1000 g. of water. Other concentrations produce proportionate rises,
i.e.,
0.26 C. for 0.50 mole per
1000
g., etc.
than
harder to vaporize the solvent from a solution from the pure solvent, so it is harder to remove it by any other means, such as freezing, and just as the boiling point of a solution of a nonvolatile substance is higher than that of the solvent, so the freezing point of the solution will be lower, and will depend, likewise, only on the number of moles of solute in a given amount of solution. The theoretical value is 1.86 C. for 1 mole of
16. Just as it is
it is
centrations.
solute in 1000 g. of water, with proportionate values at other conHere again, actual solutions show deviations from the
theoretical lowerings due to unequal attractive forces, and these deviations, as might be expected, are greater at higher than at lower concentrations, as illustrated in Table 1.
TABLE
1
Freezing Point Lowerings for
Aqueous
Solutions
0.1
Moles per 1000
g.
HO
2
0.01
1.0
Acetone,
CO(CH 3 )
0.0186
0.0183
0.185
1.79
Hydrogen
peroxide, Ethyl alcohol, C 2 6
Propyl alcohol,
Glycerol,
H2 2 H OH C H OH
3
7
0.184 0.183
0.183 0.187 0.188
1.88
1.83
C 3 H 6 (OH) 3
Cane
17.
sugar, Ci 2
2 2Oii
0.0186 0.0186 0.0186
1.79 1.92 2.06
Example: It was found that a solution of 7.29 g. of sugar in water had a freezing point 0.395 lower than that of water. What is the molecular weight of the sugar? For each 1000 g. of water in a solution of the same concentration there would be 72.9 g. of sugar. Now, 1 mole of sugar in this amount of water would produce a lowering of 1 86, and since 72.9 g. produces a lowering 95 of only 0.395, which is Pi? a e or 0.213 of the lowering produced by 1 mole, there must be only 0.213 of a mole present. If, then, 72.9 g. 9 7 is 0.213 mole, 1 mole is o .al 3 g- or 342 g. Comparing this with the
100
g. of
17
MOLECULAR WEIGHTS
by
77
analysis,
empirical formula of sugar, Ci2H 22On, as determined we see that the simplest formula is the correct one.
Exercises
(a) compounds, (b) solutions, (c) elements in terms and molecular theories. 2. What is the distinction between a mole and a molecule? Give an example of the former. 3. What conclusion can you draw from the fact that 1 liter of phosphine gas, PH 3 can be decomposed to give 250 cc. of phosphorus vapor, measured at the same temperature and pressure?
1.
,
Define
of the atomic
H
of
4. What volume of oxygen is necessary to burn 3 liters of S gas according to the reaction: 2 H 2S + 3 O 2 = 2 H 2O + 2 SO 2 ? 5. State a simple piece of evidence to show that the molecule oxygen contains two atoms.
6. If
ordinary oxygen
is
O how
2,
could you prove that ozone

are 40 g. of oxygen?
is
3?
7. 8.
(b)
gas are there in 23 g. of it? What volume would 23 g. occupy under standard conditions? 9. A closed vessel contains ammonia gas at 1 atm. and 27 C.
How many moles of oxygen, (a) How many moles of N0 2
2,
spark is passed through the gas till it is all decomposed into hydrogen and nitrogen. What will the pressure be if the temperature
is (a)
27
= N
C., (b) 127

2.
C.?
The equation
for the reaction is: 2
NH
+3H
10.
Give the
specific gravity of
each of the following gases referred
to air under the
same conditions:
.
N O
2,
2,
CO,
2 S,
C1 2
NH
3,
vapor, HC1, NO, S0 2 11. What is the volume of 34

12.
g. of
NH
at 546 C. and 4 atm.?
What would
be the relative
efficiencies of the following gases

?
as
filling for
balloons:
efficient is
2,
He,
air,
CH 4
*13.
lifting
How
hot
a balloon?
(Make
at a temperature of say 200 C., in reasonable assumptions for any further

of carbon
necessary data.)
14.
(a)
certain
compound
20%
what
of hydrogen; the atomic weights are
and hydrogen contains H = 1 and C = 12;

if
is its simplest formula? (b) What is its formula the gas occupy 1.12 1. under standard conditions?
1.5 g. of
"These are questions of greater difficulty, which should not be attacked Until the others are mastered.
78
Ch. IV
15. How many liters of measured (a) under standard 2 conditions, (b) at 22 C. and 5 atm. pressure, could be obtained by heating 1000 g. of CaCO 3 ?
CO
16. At a certain pressure and temperature 2 g. of CO 2 occupied a volume of 1250 cc. What is the molecular weight of another gas 2 g. of which occupied a volume of 720 cc. under the same temperature and pressure? 17. What volume of CO, measured at C. and 0.8 atm., could be obtained from 25 g. of carbon by the reaction 2 C + O 2 = 2 CO?
:
18.
CH
2
2,
and
19.
have a formula of the type CH, C 3H 3 etc. Given that 295 cc. of it weighs 0.317 g. at 22 C. atm., which formula is correct? Write the equation for the combustion of CO to CO 2 and
certain gas
,
is
known
to
interpret
(c)
it
in
terms of
(a)
moles,
(b) liters
at standard conditions,
grams.
20. 4.0 g. of scandium react with an excess of HC1 to give 3.054 C. and 760 mm. At. wt. of Sc = 44. (a) liters of hydrogen at What weight of scandium is equivalent to 1 g. of hydrogen? (b)
What is the formula of scandium chloride? (c) What would be the volume of hydrogen at 25 C. and 784 mm. if collected over water? Vapor pressure of water at 25 C. is 24 mm. 21. What is the formula of a gas containing 46.1% of carbon and 53.9% of nitrogen, 2.60 g. of which has a volume of 560 cc. at 0C. and 2 atm.?
22. If grams of a gas occupy 22.4 liters at 1 atm. and 273 K., what volume, v, will grams of it occupy at p atm. and r? *23. Hydrogen peroxide contains 1 part by weight of hydrogen to 16 parts of oxygen, and a solution of 0.369 g. of it in 25 g. of water 0.805 C. What is its formula? had a freezing point of
The following gas reactions are carried out in closed vessels at constant temperature. If the initial pressure is 1 atm., kept = I2 what will the final pressure be in each case? (a) 2 HI 2 = 3 2 (c) 4 PH 3 = P 4 6 2 (d) 2 SO 3 = 2 SO 2 O 2 (b) 2 O 3
24.
+H
2.
+ H
,
*25.
Arrange the following gases

still air:
diffusion through
*26.
NH
in order of increasing rate oi
3,
C1 2
COC1 2
H H^, SO
2,
radius of a helium atom is approximately 10~ 8 cm. What fraction of the volume occupied by helium gas at 1 atm. and C. is actually occupied by the atoms themselves?
The
*27. Calculate the ratio of the density of air containing 0.01
mole per cent of C1 2 to that of pure air at the same temperature. 28. What volume of liquid benzene, density 0.82 g. per cc.,
MOLECULAR WEIGHTS
would be formed by condensing
1
79
1 liter of benzene vapor, measured atm.? Benzene, C 6 H 6 29. 68,000 calories of heat are given out when one mole of hydrogen burns. How many calories are liberated by the burning of the hydrogen in a soap bubble of 500 cc. volume? Assume 1 atm. pressure and 25 C.
at 100 C. and
*30.
AsH
is
of
Mg3As 2 would be
toxic at a partial pressure of 0.04 mm. What weight necessary to infect one cubic meter of air to
this concentration?
*31. In deriving the number 28.8 for the weight of 22.4 1. of air at standard conditions, in paragraph 8, the presence of argon was neglected and the fraction of oxygen molecules was taken roughly
as ^. Calculate a more accurate value from the following figures for the per cent of each kind of molecule: 78% 2 21% O 2 1% A.
pressure of water vapor at 20 C. is 17 mm. Calculate the weight of 1 1. of (a) dry air at 20 C. and 760 mm. (use the result of exercise 31), and (6) air saturated with water vapor at
*32.
The
the
same temperature and
pressure.
C. is 1.206 of the 2 at 200 atm. and 20 value of pv at low pressures and the same temperature. What balloon capacity could be filled by the hydrogen in a steel "bottle" of 1.00 cu. ft. capacity and a pressure of 200 atm. at 20 C.?
*33.
The value
of pv for
*34. How many molecules of gas per cc. are there in an X-ray tube evacuated to a pressure of 10~ 6 mm. at 20 C.?
CHAPTER V
THE RELATION OF CHEMICAL PHYSICAL PROPERTIES TO ATOMIC STRUCTURE
AND
1. The nature of chemical union prior to the last few decades was clothed in mystery. Such pictures of it as were drawn were the product of pure speculation. The older generation of living chemists had to accumulate their knowledge of chemical behavior piecemeal, with little to guide them in the way of general principles. The students of today, however, can be saved much of this long process by availing themselves of the deductive approach made possible by the flood of light recently thrown upon the structure of matter. This chapter is intended only as a preliminary survey, details and proofs will be given later, particularly in Chapters XVI and XVII. The student should not be discouraged if he should feel after studying it that he is far from being expert in understanding atomic structure and relating it to chemical
and physical properties. That facility is something to build up gradually by repeated practice in connection with an ever-widening range of phenomena, not a task that can be
completed in a few lessons. There are three common ways of presenting a subject. They may be designated, respectively, the logical, the chronological,
and the psychological. The
up an argument, step by It is the form which a subject finally assumes in an orderly mind, the one, therefore, which it tends to assume in a
textbook.
consists in building step, each complete and conclusive.

first
The second way
follows the historical order in
which the subject was developed. This is likely to be interesting and worth retracing, but it may not be the most sig80
PROPERTIES
AND STRUCTURE
81
to the learner because the clearest experimental evidence has not always been the first to come to light. The way which is here called the psychological way takes account of the fact that a scientific principle is usually not a simple
nificant
proposition to be grasped the moment strated, but rather a concept, which
it is
logically
demon-
may have many and
far-reaching implications. To use it with true understanding requires skill only to be developed by practice. It is like an
which cannot be acquired by explanations and demonstrations alone, but by repetition under increasingly difficult conditions.
athletic skill, such as diving,
TABLE
1
Ultimate Particles
Atomic weight
O =
Electric charge
16.0000
Unit
1.60
10~ 19
Radius, cm.
coulombs
Electron
Proton
Neutron
cf.
Oxygen atom
0.000,548 1.0073 1.0087 16 0000
> 10~
2 2
13
+1
6000
X X X
10~ 13 10~ 13 10~13
is neither logical nor chronological; it is a sort of brief aerial reconnaissance of scientific territory of great importance to students of physical science. It gives a
This chapter
preview of what is to be later proved by evidence and logic. The student will have repeated opportunity throughout the course to learn to find his own way about in this region. 2. Ultimate Particles. We now have abundant evidence that
the atoms are not the ultimate, indivisible particles they were once conceived to be, but are composed of still smaller particles. The most significant of these, according to present views, are the electrons, protons, and neutrons. Their significant properties, mass, electric charge, and size are given in Table 1. The figures for size are to be regarded as somewhat uncertain, for they depend on the method used in calculating them. The
properties of the electron are such that a definite radius cannot be measured; all we are justified in saying is that an electron
occupies
much more
space than a proton or a neutron.
82
Ch.
3. Composition of Atoms. The atoms of the different elements are all made up of these three kinds of elementary particles. The weight of an atom depends almost entirely on the number of protons and neutrons it contains, since the
electrons are so light that they contribute but
little
to atomic
weight. The charge of an atom, however, is not affected by the number of neutrons present but depends on the balance neutral atom contains the between electrons and protons.
same number of electrons and protons; an atom with unit negative charge has one extra electron; one with unit positive
charge has lost one electron one with 2 units of positive charge has lost 2 electrons, etc. 4. Structures of Atoms. The protons and neutrons in an atom are packed tightly in a very small nucleus around which the electrons travel at relatively great distances, a little like the planets of the solar system, which travel around the sun. The size of the solar system is fixed by the planetary
;
orbits, its
A neutral
of the
is
mass mainly by the mass of the sun. atom of oxygen, for example, has 8 electrons and
8 protons. Since its atomic weight is 16, it contains 8 neutrons in addition to its 8 protons in the nucleus. If the diameter
whole atom
;
is
called
1,
the diameter of the nucleus
the diameter of a single electron is perhaps, If the nucleus is represented by a small pea, roughly 0.001. the electrons could be large oranges, the farthest 100 yards
only 0.0001
away from
since
it
the pea. It would be a queer kind of pea, however, would weight about one ton if the oranges were ordinary oranges. It is evident that an atom, like the solar
system, is mostly empty space. 5. Electron Orbitals. The Danish physicist, Bohr, assigned definite circular and elliptical orbits to the electrons, on the
basis of certain assumptions, but it is now realized that it is impossible to verify these orbits experimentally. The orbit of a comet can be fixed from a series of observations
of its successive positions, but anything we do to an electron to find out where it is diverts it from its path, and we can
never find out where
it
would have been
later
if left
alone,
PROPERTIES
AND STRUCTURE
83
It is possible, however, in effect, to shoot electrons at a great many atoms of one species and learn how the percentage of successful hits on the electrons of the atom varies with
the distance from the nucleus.

probability or 'electron density*' varies with the distance. The results of such experi'
Figure
shows how
this
ments and calculations permit the drawing of the only

kinds of atomic pictures that have any actual significance. Figure 2a shows such a picture. It
is
05
Angstr0m
10 i~o
units
8
Ts
a picture such as
if
Distance from nucleus in
= 10" cm) were pos(1 Angstrom unit Electron density in a hydrosible to take a photograph Fig. 1. * en atom at var y> n s distance from its of the electron of a hydroJ nucleus. gen atom by time exposure without disturbing it. The electron appears to be moving in and out from the nucleus in different directions, giving " the effect of a spherical "cloud. Figure 2b shows the "cloud" for an electron which is temporarily moving in
Would
result
it
Fig. 2.
"Electron clouds."
a state farther from the nucleus. It will later revert to the
more
1
stable state, emitting a
"quantum"
of radiant energy
of definite frequency. Figure 2c shows the dumbbell shaped " 'cloud made by an electron moving in still another tempo-
rary state in a magnetic
field.
84
Ch.V
6. The Grouping of Electrons in Atoms. The number of neutrons in the nucleus of an atom, while contributing to the atomic weight, has little effect upon its chemical behavior. This is determined by the nuclear charge, which depends on the number of protons. The nuclear charge fixes the number of electrons required to give a neutral atom, and these electrons arrange themselves in certain stable groups. The elements known as the "noble gases" are inert chemically on
account of their stable
electron
arrangements.
Table 2
shows these groupings.

TABLE
Electron Groupings in the
2
Noble Gas Elements

Argon
Krypton
Helium
Nuclear charge atomic number
(No. of protons]
Neon
Xenon
Radon
+2
No. of electrons
1st
group
K
L
2nd
3rd 4th 5th 6th
M
N
O
P
222222 88888
8
18 8 18 18 8
18 32 18
+10
+18
+36
+54
+86
We
see that 2 electrons

all
form a stable group nearest the
nucleus in
these atoms. All but helium have stable octets
need not bother at this time as their outermost groups. to discuss the significance of the buried groups of 18 and 32,
shall focus our attention on the pair and the octet. 3 shows the probability of finding an electron, or the Figure density of the "electron cloud" at different distances from
We
but we
the nucleus for an atom of krypton, which has 2, electrons in the K, L, M, groups, respectively.
8,
18, 8
7. Gain or Loss of Outer Electrons. Elements with intermediate atomic numbers have either too many or too few electrons to give these stable groupings. Table 3 shows the distribution of electrons in the elements with nuclear charges from 1 to 20. These nuclear charges, serving as they do to
PROPERTIES
AND STRUCTURE
numbers
orient the series of elements, are called atomic
The elements not possessing the stable outer electron groups shown in Table 2 tend to acquire these groups by gaining or
losing electrons, as the case
may
be.
The element
fluorine,
whose electron groups are 2,7, could assume the neon structure by acquiring an extra electron, but since its nuclear charge is only + 9, the electrons 2,8, would give the resultant atom a unit negative charge, which we write F~ and call
0.5
J.O
1.5
Distance from nucleus, Angstroms

Fig. 3.
"Electron density" for a krypton atom.
has 2,8,1 electrons, and can its outer electron, making Similarly, magnesium, Mg, can become aluminum, Al, can become Al^*; oxygen, 0, can Mg++; etc. The elements near argon, A, can assume become O the argon structure, 2,8,8, by gaining or losing electrons, as the case may be, giving S Cl~, A, K+, Ca,++ etc., all having 2,8,8 electrons. Lithium, Li, becomes Li+ in assuming the helium structure. Hydrogen, like Li, Na, K, can lose its only electron, since it is not part of a pair or an octet. This is so important that it is summarized for the first 20 elements, in Table 4, for emphasis. 8. Chemical Reaction by Electron Transfer. Atoms which
fluoride ion.
Sodium, Na,
11,
assume the neon structure by losing it Na + sodium ion.

,
can lose outer electrons can react chemically with atoms which
86
PROPERTIES
AND STRUCTURE
87
can gain electrons, giving charged atoms which can arrange themselves in solid crystal lattices. If we represent a fluorine
atom by
tne circle inclosing what
is
called
the
"kernel/' consisting of the nucleus and the inner pair of

electrons, the part not disturbed in chemical reactions,
TABLE 4
whose
Gain and Loss
of Electrons to give Stable Structures
Mg
2
Al
2 8 3
8
2
Mg++
2
Al
2
8
Sc
2
Ca
2
8 8 2
8 8 3
Sc+++
2 8 8
2
8 8
charges add up to
7,
and, represent a sodium (natrium)

kernel consists of the nucleus, the
atom by ~(+^)> whose
inner electron pair, and the electron octet, whose charges add up to + 1, then the chemical reaction between these two atoms may be represented as follows:
=
(+7)" and
give
(+7)
and (+1)
These resulting charged atoms, F" and Na+, attract each other, and, if there are many of them, build up a cubic crystal lattice in which the oppositely charged atoms alternate as illustrated in the one in Fig:. 6 labeled "ionic." Sodium
88
Ch.
chloride crystals,
this plan.
If
common
salt,
NaCl, are constructed on
fluorine atoms are used, one atom of with its two outer electrons, can satisfy two the former, fluorine atoms. The reaction can be pictured as follows:
magnesium and
and
"
"
and
~@^
to
The
resulting
MgF2 necessarily
forms a somewhat more com-
plicated crystal lattice than the simple cubic mentioned above. It can be seen, in general, that the numbers of outer
atoms combine, their combining values, or "valences" (cf. Chapter IX), and allow us to write compounds of the elements in Table 4, such as: KC1, CaCl 2 ScCl 3 K2 S, CaS, Sc 2 S 3 The outer electrons of an atom, the ones which are involved in chemical changes,
electrons determine the ratios in which
,
, .
are called
its
valence electrons.
clearer for future
in the following
The terms we have been using may be

Use
if
summarized
diagram.
Kernel
Valence electrons
9. It is often
convenient to represent the kernel of an atom
symbol in boldface type, remembering the + charge each kernel would have and the outer electrons that would have to be present in a neutral atom. The following comparison illustrates the relation between these kernel symbols and the ordinary symbols, using dots to denote valence
by
its
electrons.
Ordinary symbol Kernel symbol
H
H-
H+
Cl
-Cl:
Cl~
:
C1 2
1:C1:
HC1
H:C1:
HO
2
:cj:
H:6:
ii
10
10.
PROPERTIES ANID STRUCTURE

Electron-Shared or Covalent Bonds.
89
crystalline
Many
salts are held together
by
Na+ and
F". There
is,
"ionic" attraction, like that between however, another type of strong chemi-
cal bond. Its simplest example is the hydrogen molecule, H2, which is made up of two protons and two electrons. Let us
list, in increasing order of stability, the various ways in which these four particles could be assembled. The least stable (i.e.,
that in which the four particles are one of the electrons combines with one completely separated. of the protons to form a hydrogen atom, 314 kcal. of heat is liberated. If both electrons are acquired by one of the protons, the resulting system (H + H~~) is somewhat more stable, 331
highest energy) state
is
If
kcal. being liberated in its formation. Of still greater stability (374 kcal. evolved) is the system in which the two protons to-
gether have one electron moving around and between them, so as to form the charged molecule H2 + The next more stable
.
state (627 kcal. evolved) comprises two hydrogen atoms, each proton having acquired one of the electrons. The stablest state
of
in
all (731 kcal. evolved) is that of the hydrogen molecule, H2, which both electrons simultaneously are moving around and between the two protons. The stability of molecules such as H2 + and H2 can be ex-
plained by the electrostatic attraction of the positive nuclei for the negative electrons. This attraction is considerably greater than the repulsion of one nucleus by the other, or of
the two electrons by each other. We may say that the nuclei are held together by the electrons, which spend a substantial portion of their time in the region between the nuclei, and so
act as a sort of "electrostatic glue." Our concept of a hydrogen molecule must therefore be two protons with two electrons
moving about both
of
them
in
some
sort of stabilized orbits,
similar stability is giving a "cloud" shaped like Fig. 4. achieved by the pairing of the odd electrons of 2 chlorine atoms. Unable otherwise to gain undisputed possession of 8 electrons,
they satisfy their need for 8 electrons by going into partnership,

as represented
by
:C1:C1:.
...
,
We
,
have such pairing and sharing
also in the molecules:
F2 Br2
I2 .
90
Ch.V
11. Electron-pak bonded molecules can be very stable, as illustrated by the heat necessary to dissociate them into
atoms, shown in Table
5.
The
figure for
NaCl vapor
illustrates
the fact that electrostatic bonds and

electron-pair bonds can be of comparable magnitude.
Fig. 4.
occur, at least with any Electron "cloud" strength, in the case of the larger, metal-
_
a
Metals and Nonmetals. The pairof the outer electrons of two like ing atoms that we see in the molecule, H2,
12.
does
\{ c
not
density for molecule.
hydrogen
atoms, whose valence electrons, even

s tate, are
more or
less free
within the metal, in consequence of which they are electric conductors. The ability of metals to reflect light
to
move about
from their
surfaces, called metallic luster,

TABLE
5
'
is
due to these loosely
Heat
of Dissociation of
One Mole
I2
into
Atoms,
Kilocalories
H2
F2
C1 2
103.7
37.7
Br2
NaCl(gas)
45.2
35.4
100.
56.9
held electrons. These electrons can easily be detciched from the solid metal, the work required in the case of sodium being
only 48 kcal. Elements whose outer octets are complete, either alone, as with the noble gas atoms, neon, argon, etc., or by sharing, as with Cb, C>2, N2, etc., hold their electrons so firmly that they are nonconducting and nonmetallic in the solid state. The work of removing an electron from a molecule of gaseous Cb is 304 kcal. per mole.
13. Nonpolar, Polar, and Ionic Compounds. As stated above, two like atoms usually combine by sharing outer
electrons,
illustrated
if
possible, so as to complete pairs and octets, as by chlorine in Fig. 5. The molecule is symmetrical
and electrically neutral, and is called nonpolar. If the atoms differ somewhat in their affinity for electrons due to differing
sizes or structures,
the bonding or shared electrons will be
14
PROPERTIES
AND STRUCTURE
91
closer to, or
spend more of the time traveling about one atom than the other, making this atom on the whole more negative, as illustrated by iodine chloride, Fig. 5. Such a molecule
called polar.
If
is
the difference in electron affinity
is suffi-
ciently great, the outer electrons of the one
may
be completely
CI-CI
I-CI
Polar
Na+Cr
Ionic
Nonpdar
Fig. 5.
Types
of molecules.
lost to
the other so that there
is
no true chemical bond but
only the electrostatic attraction of the now positive and negative atoms for each other, as illustrated by sodium chloride.
Such a molecule is called ionic, since the two parts are easily detached from each other on going into solution where they
are free to
14.
wander
off in different directions.
The
charges in
and degree of polarity, or displacement of a molecule is expressed by its dipole moment.
The
dipole moment of a molecule determines the force which an electronic field can exert to orient the molecule, as shown
in Fig. 6. It obviously depends upon the magnitude of the charge separation in the molecule, i.e., it is greater the larger
the charge difference between different parts of the molecule
and the distance

in
of separation.
The
transition
from nonpolar
is
through increasingly polar to ionic compounds Table 6.
illustrated
The dipole moment often gives important evidence of molecular structure. For example, the large moment of the water molecule shows that it is not linear and symmetrical
as represented
represented
of a linear
by HOH, but approximately right angled, as by HO. If we represent the charge distribution
form by + -O= + we see that the protons (hydro-
gen nuclei) cancel each other, while a right-angled arrange-
TABU
figures are for dipole
Ch.V
Polarity
(The
moment
10 18 electrostatic units)
Electron displacement
ment
-f
= throws the positive charges to one
side,
the negain
tive to the other so that the molecule

electric field as
would tend to orient
an
shown
in Fig. 6.
Three
Effects of
Field
an Electric on Molecules
Calculated from dielectric constant,
formula, v(
and the volume per mole,
v,
!)/(
+ 2).
Fig.
by the
15
PROPERTIES
AND STRUCTURE
93
A study of dipole moments indicates that the negative character of some of the commoner elements increases in the following order:
K, Na, Ba, Ca, Mg, Al, Sn, Sb, B, As, H, P, N, O, F.
I,
S,
C, Br, Cl,
15. Types of Crystal Lattices. The various types of atoms and molecules arrange themselves in solid crystal lattices
of rather distinct kinds with characteristic properties. Metallic atoms hold their electrons so loosely that even when massed
together in the solid form the electrons can migrate more or less freely through the solid under the impulse of an electric field giving metallic conduction, the most distinctive property of metals. This is crudely illustrated in Fig. 7.
Moreover, since the positive
"kernels" of the atoms

electrons
are
the
atoms stripped
to each other
of
their
outer
not
bound
by specific bonds, they can be displaced relato each other without destroying the general attraction tively between kernels and electrons; hence the metals are ordinarily malleable.
on the other hand, form crystals with atoms or, better, ions, which are too alternately to change places unless the structure is melted and large
Ionic substances,
and
greatly
solid
expanded; hence they are nonconductors in the form but conductors in the liquid state. To split the
crystal requires the overcoming of the electrostatic forces between the ions. They are not malleable or plastic since the sliding of one layer over another would bring together ions of like sign which would repel each other resulting in breaking
the crystal before a new position of attraction is attained. Nonpolar molecules and the single stable atoms of helium,
neon,
argon,
etc.,
exert
no
electrostatic
attractions
upon
each other but only a relatively weak force due to a general interaction of the rapidly moving electrons of one molecule with those of another, analogous, very roughly, to the interaction of vibrating tuning forks. Nonpolar substances, therefore, are relatively soft, and are easily melted and vaporized-
94
Ch.V
00
....
a. Metallic
-f
e
b. Ionic
888 8888
c.
G
d. Molecular, polar
e.
Molecular, nonpolar
Diamond
Fig.
7.
Types
of crystal lattices.
number
of the lighter molecules exist as gases at ordinary
temperatures and pressures. Figure 7 includes a crude picture of a lattice of nonpolar molecules, e.g., Ck.
If
we may expect them

together,
the molecules are more or less polar like IC1, in Fig. 5, to strive for crystal arrangements in which
oppositely charged parts of molecules are as near as possible

giving enhanced attractions, melting points and crystal strengths, other things being equal, as in Fig. 7, for polar molecules. In the liquid state, unlike the ionic substances, they cannot conduct the electric current by migrating independently to the poles, but they will tend to orient,
except as opposed by thermal agitation, so that the charged ends of the molecules will lie in the direction of oppositely charged plates thrust into the liquid, as illustrated in Fig. 6.
effects of applying electric the displacement of electrons with respect to nuclei; the second, the stretching or bending of molecules, called atomic polarization; the third, the orientation of dipoles already existing within the molecule. The disillustrates
fields
This figure
three
to molecules.
The
first is
tinguishing characteristics of each effect are stated.
16
PROPERTIES
AND STRUCTURE
type
exists,
95
One other important
lattice
that represented
by diamond. Carbon atoms have 4 outer electrons, as shown in Table 1. When 2 such atoms form a chemical bond by sharing a pair of electrons the possibilities of sharing are not exhausted, as they are with chlorine atoms, but each can form electron pairs with 3 other atoms. The result is represented in 2 dimensions in Fig. 7, "diamond lattice." Actually each atom has 4 others around it arranged like the corners of a tetrahedron as illustrated in Chapter XVIII, Fig. 1. We see that there are no molecules of carbon in such a crystal, but that all the atoms are firmly bound together
with electron-pair bonds, continuing throughout the crystal. scratch or split such a crystal would require the rupture of a large number of these bonds, which are particularly strong with carbon due to its small atomic size. In fact, carbon is the hardest known substance, and neither dissolves nor
To
vaporizes at any ordinary temperature. 16. Relative Stabilities of Ionic Compounds. In the cases
of
which the atoms may be regarded as defior negative by reason of the passage of elecnitely positive trons from the metallic to the nonmetallic atoms, we may relate the stability of the compound in large part to the
compounds
in
ease with
which the electrons can be detached from the former and acquired by the latter. If the formation of one compound from its elements liberates more energy than the formation of another, it is evident that to recover the free elements from the former would require more energy, whether electrical or chemical, than in the case of the latter; the
former is therefore more stable. This energy of formation may be divided into a number of parts corresponding to carrying out the synthesis in a number of distinct steps. For example, if one mole (58.5 g.) of solid sodium chloride
to be synthesized from solid sodium and gaseous chlorine, instead of allowing the elements to react with each other directly to form the salt, a process which liberates 98 kg.
is
cals. of
heat per mole of NaCl, it is possible to melt one gramatom of sodium, Na (solid), with absorption of its heat of
96
PRINCIPLES Of CHEMISTRY
Ch.
fusion, next to vaporize it to give gaseous atoms, Na (gas), absorbing its heat of vaporization, then to strip it of its outer
electron, giving
Na+
(gas),
then
(gas)
let it
unite with Cl~ (gas),
prepared by splitting
CU
into atoms,
Cl (gas), and
molecules,
adding an which are then
electron per atom, to give gaseous

liquefied,
NaCl
and
finally solidified.
This synthesis in steps is indicated in the following diagram along with the amount of heat, in kcal., involved in each step. A sign means that heat has been absorbed, increasing the heat content of the material involved, and a sign that heat has been evolved or
lost.
TABLE 7
I2
(solid)
Na
i
(solid)
JQ 2
(gas)
+26
(gas) (gas)
j
Na
|+29
CP
1-128
NaCl
NaCl
(gas)
j+119
Na+
Cl (gas) - 92 I
(gas)
K (solid) |+22 K (gas) 1+101

K+
(gas)
.
I
l2
+7
(gas)
|+18
I
(gas)
|-79
|
F (gas)
105
KI
I
(gas)
|-52
Total
-43
- 98 kcal.
(solid)
KI
(solid)
79 kcal.
the different steps for the two substances, sodium chloride, iodide, KI, it can be seen how differences between the several respective steps affect the total.
By comparing
NaCl, and potassium
For example, the greater total heat of formation of NaCl
is
due
in
;
part to the much greater heat evolved when its gaseous ions unite they are smaller and can approach closer to each other. The totals
are
by the greater heat absorbed in the electron from the gaseous metallic atom, in the case removing of the sodium, and in the other direction, by the greater heat
evolved upon adding the electron to the nonmetallic atom, in the case of chlorine. The smaller energy involved in vaporizing the metal in the case of potassium contributes to the stability of its
made
to differ in one direction
compounds.
17
PROPERTIES
may
AND STRUCTURE
be clearer
if
97
These comparisons
the magnitudes are
represented graphically to scale, as in Fig. 8. Each step which naturally evolves energy is represented as occurring
downward, while each step which absorbs energy as occurring upward. The net evolution of energy on forming
a compound
of all the
is
is
represented
thus the excess
downward over the w upward processes. The greater the evolution of energy when
the
No"
compound more stable it

would have
in
is
is,
formed, the because this
to
be
expended
compound separating again into its elements. The diagram shows that the main
"downhill" steps are bigger for forming KF than for forming KI, and, conversely, that to
kF
the
KI
Nol
Kl(s)
No
Nol(s)
decompose KF would require more energy than to decompose
KF()
135
Fig- 8.
79
70
Graphic representation of KI, principally because, 8tepB involved in hatl first, more energy is required to "lift" apart K+ and F~ than + and I~ the former are closer together and, second, because it takes more energy to "lift" the electron from F"" than from the larger I~~. If we compare KI and Nal, where
the difference
electron from
lies
in the metals,
we
see that "lifting" the
a K-atom requires less energy than to "lift" one from the smaller Na-atom, hence more energy is left over to be evolved when KI is formed than when Nal is formed, and, conversely, more would have to be expended to get K and I 2 from KI than to get Na and I 2 from Nal.
be rather disappointing at this early stage to many factors have to be considered in order to make accurate predictions. Most of us would prefer to
17. It
may
learn that so
98
Gu V
have the matter much simpler. Some profess to predict the weather by looking at the new moon, to see whether its horns point up or down. Some are impressed by claims that a single patent will cure many ailments, from dandruff down to athlete's foot. There are people who vote for a candidate
who promises to bring prosperity by means of some single, simple formula. The trouble is that matters are seldom so simple. The weather forecaster, spending all his time on the
job, using a variety of criteria, still makes mistakes. Individuals and society spend part of the time recovering from the
most part, learned to be about explanations that are too simple. They have sceptical now found that there are 98 elements, not four, "earth, air, fire, and water"; that the law of gravitation is not an adequate basis for a system of physics; that the behavior of electrons cannot be* predicted from that of baseballs. Political and economic problems are still more complicated, and we should learn to distrust the social scientist who offers in a single palatable and intoxicating elixir to cure a sick social and economic system. We should learn that a spree and a cure may begin with similar feelings of elation but they end
very
18.
effects of absurdly simple panaceas. Physical scientists have, for the
differently.
Electrochemical Series.
It
may be worth
while
to
simplify a problem provided we remember what we have done and do not rely too heavily on the result. We decide in
the morning whether or not to take along an umbrella on the basis of an admittedly unreliable prediction regarding the
weather. After
all, most of us can do better than tossing a coin to protect ourselves from getting wet. Indeed, the making of an accurate analysis of a problem may take so long, even when we know how, as not to be worth the effort.
We
we can correlate chemical stabilities with only a small proportion of error if we focus our attention on only a few of the factors presented in paragraph 16. In that case it is important only not to be surprised if we make a few mistakes.
find, fortunately,
that
19
It is
PROPERTIES
AND STRUCTURE
99
stability of
evident from the values in Table 7 that, while the a compound depends upon a number of factors,
the
electron
changes are
in
comparatively
losing
will
large;
hence
the
energies
involved
gaining and
electrons
largely
be discussed at more length later (Chapters XVI and XVII) in relation to atomic structures, and we will content ourselves here with simply giving a list, in Table 8, of some of the elements arranged roughly
determine
stability.
This
TABLE
Heat Evolved
in
Formation of Compounds in Kcal. per Gram-atom of Negative Element

Cxides
Chlorides
Iodides
Potassium
Sodium
Calcium
Aluminum
Zinc Iron (ferrous)
Tin (stannous) Lead Hydrogen Copper (cuprous)

Silver
86 99 152 133 85 64 70 52 66
105
40
7
98 104 56 49 41 40 43 41 33 30
10
79 70
64 24
25 24
18
20 6
16 15 2
Gold (aurous)
according to the stabilities of their compounds. The order is not quite uniform because the charged atoms do not arrange themselves in the same patterns in crystals of different comof
pounds, but the only great discrepancies are in the positions Na2 O and 2 O.
19.
The
order of the elements in Table 8

will
is
worth remem-
not be difficult for one who will see its correlation, first with its historical significance. The noblest metal in the list, gold, has the greatest tendency to retain its electrons in the metallic state rather than to become
bering. This
positive in
known from
compounds, and, accordingly, has doubtless been earlier times than any other metal. Neither gold nor silver, however, were sufficiently abundant to have any great cultural significance. Copper, on the other hand, is
100
Ch.
more abundant and

the
first
is easily obtained from its ores and was metal to play a significant role in making tools and utensils. The alloy of copper with tin gave bronze, which is harder than either, and gave rise to the "bronze age." Iron is harder to obtain, hence the "iron age" came later. Only in recent times have metals such as sodium and aluminum been obtained. The order of the elements in Table 8 can be
further correlated with their ordinary properties and uses. For example, gold is not subject to corrosion, silver tarnishes
slightly, copper and lead more readily, but they can still be used where iron would rust badly. Aluminum seems to be stable but this is because the thin oxide coating first formed
very adherent and impervious; if the surface is wet with mercury the film no longer adheres and the metal oxidizes with great rapidity. 20. Salts. Substances which crystallize in ionic lattices,
is
except those whose negative ion

salts,
is
OH~,
salt.
by analogy with NaCl,

less soluble in
common
are usually called Most of them are

.
water, whose polar molecules (cf paragraph 12) are able to attract the ions of the salt crystal sufficiently to overcome the forces holding them in the lattice.
more or
They
The
are then able to
wander about independently
in the
solution
(cf. Chapter VIII). ions of salts are not confined to single charged atoms, but may consist of charged groups. Figure 10, Chapter XXIII,
where the ions are Ca"

spectively.
represents the structure of such salts as 1 4 and COa or

" "
CaCOs and NaClOa,
Na+
and ClOa",
re-
The
following polyatomic ions are frequently en-
countered
SOs SO*
sulfite
C2H3O 2
ClOa""
acetate
chlorate
sulfate
carbonate COa NOa~ nitrate
CIO""
hypochlorite
"
l
ammonium NH** Ag(NH 3 )2~ silver ammonia

ions,
complex.
Such
ions, like
monatomic
owe
their charges to
an excess
or deficiency of electrons.
21
PROPERTIES
AND STRUCTURE
101
21. Acids. There are a number of hydrogen compounds which, although not giving ionic lattices, react with water + to give hydrogen ion, which may be written 3 O+ (aq.), 4 + but is usually abbreviated to the H2O ), (i.e., understood. Such a solution is water of hydration being
+H
",
taste,
readily recognized as acid by such familiar tests as sour reaction with base metals, such as zinc, to produce
+ Zn = 2 Zn++; reaction with a carhydrogen, 2 bonate to produce CO2 gas, 2 H + CaCOs (solid) = Ca+ + H 2O CO 2 and colors imparted to certain highly colored substances called indicators (cf. Chapter XIII). There are a number of more or less familiar acids which we may recall
H +
;
H +
and characterize
briefly.
Hydrochloric acid, HC1,
is
a gas
when
but
it
in the
is
pure state at ordinary pressure and temperature, very soluble in water, forming the solution known
is
2 SO4, in the a dense, syrupy liquid, and has the trade
industrially as "muriatic acid." Sulfuric acid,
absence of water,
name, "oil of vitriol." It is manufactured in larger quantities than any other substance for purely chemical purposes. Nitric acid, HNO 3 is a fuming, corrosive liquid extensively used to dissolve the nobler metals and in the manufacture of explosives. Acetic acid, HC2H 3 O2 (only one of the hydrogen atoms of which has acid properties), is the acid of vinegar.
,
Phosphoric acid, H 3 PO 4 is used in the phosphate drinks at soda fountains. Boric acid, HsBOa, or "boracic acid/' is a solid giving a solution of very faintly acid properties. It finds use as a mild antiseptic. Oxalic acid, H 2 C2C>4, a solid in the pure state, finds frequent use as a chemical reagent. The
,
various fruit juices contain characteristic acids, such as citric acid, found in lemons, tartaric acid in grapes, malic acid in
apples, etc. When acids dissolve in water, there is formed, along with + an equivalent amount of negative ion, e.g.,
HC1
2
HNO H SO
(gas)
3
(liquid)
(liquid)
= H+ + C1-, = H+ + NO 3 -, = 2 H+ + SO4~.
102
22. Bases.
Ch.
Certain solid lattices contain the hydroxide which is liberated, if the substance is soluble, on going into water solution. Such substances are called bases. The positive ion is nearly always that of a metal. Most of
ion
OH~
are insoluble in water, or nearly so, the chief exceptions being sodium hydroxide, NaOH, sometimes called "caustic soda," potassium hydroxide, KOH, sometimes called "caustic
them
potash/' the solution of which is often called "lye," and barium hydroxide, Ba(OH) 2 Calcium hydroxide, Ca(OH) 2 "slaked lime/' is sparingly soluble; its solution is known as "lime water." To these should be added ammonium hydroxide,
.
,
NH
water.
OH, formed when ammonia gas, NH 3 The soluble bases, especially the first
,
is
dissolved in
two, are often
called alkalis,
and
their solutions alkaline.
The most
significant property
common
to. bases is their
ability to neutralize acids. If the base and acid are both soluble and largely split into ions, the reaction is simply,
H+ + OH~ = H 2 0. If the base is insoluble, for example, Pb(OH) 2 and the acid soluble, the reaction is expressed by Pb(OH) 2 + 2 H+ = 2 H 2 O + Pb++. Of course, in order to have a solution of H+ some negative ion must be present;
,
e.g.,
N0 ~,
is
there
but where this does not take part in the reaction 3 no more necessity for representing it in the equation
is
than there
to include the vessel, the operator, or other
necessary concomitants; nevertheless, it is often important not to forget its presence in connection with any later treat-
ment
(2
of the solution.
Some
represent the above
teachers, for this reason, prefer to reaction by the equation, Pb(OH) 2 -j-
2 2O 3 8 "). (Pb++, 2 soluble bases, like acids, can be recognized by the colors they give to indicators. shall see that it is possible
H+, 2
NO ~) =
NO
The
We
by selecting proper indicators to construct a scale to measure all degrees of acidity and alkalinity (cf. Chapter XIII).
23. Basic
and Acidic Oxides; Anhydrides

e.g.
of
Bases and
Acids. Certain oxides of metals can react with water to
produce bases,
CaO +
= Ca(OH) 2 =
Ca++
OH",
24
or,
PROPERTIES
they
AND STRUCTURE
103
or, again,
remain after a base is dehydrated by heating; they may neutralize an acid directly, without first 2 H+ = H 2 O Ca++. Their reacting with water, e.g., CaO
may
justification for calling them basic oxides or basic anhydrides, or even, briefly, bases.
close relation to bases
is
Certain other oxides, chiefly those of nonmetals, react SO 3 = H 2 SO 4 = 2 H+ with water to yield H+, e.g., 2O
SO 4
24.
hence
may
be called acidic oxides or acid anhy-
drides.
Other Systems of Acids and Bases. The definitions of
acids and bases given in this chapter are the ones most gen-
where remost attention are those occurring in aqueous solutions. Acids and bases are substances that can + and OH~, the ions of the solvent, give, respectively, H H 2 O. Other points of view have, however, proven useful for dealing with other classes of compounds and reactions. In dealing with reactions in liquid ammonia, a solvent showerally used, particularly for inorganic chemistry,
actions
receiving
ing
many
similarities with water,
it
is is
desirable to use the
"ammonia system/*
in
which an acid
4 +, and a base any gives the positive ion of the solvent, ~ substance which gives its negative ion, Neutralization 2 ~ = + 2 The organic chemist has for is 2 3 4
NH NH
any substance which
NH + NH
NH
study a large number of acids which give H+ but few bases which give OH~, and he uses a variety of solvents, hence he usually prefers a system which is not restricted in these respects: one which defines an acid as any species, whether charged or uncharged, which can give off a proton, H+, and a base as any substance which can unite with H+. Thus + are all H 2 CO 3 HSO 4~, and 4 acids, by virtue of the
,
NH
3
reactions:
and
HCO3~,
H C0~ = H+ + HSO = H+ + SO 4 NH + = H+ + NH SO 4~~~, and NH are all bases,

2 4
",
3,
though varying
is still
widely in strength.
A fourth
system
is
used which
more
104
it
Ch.
general, in that the criterion of
+ as escapes also from the limitation of an acid. For over a century chemists have
to
been
accustomed
"
speak of
"basic
oxides"
and
"acid
oxides,
influenced
by
the close resemblance between the neuacid, such as

4
tralization of a base
and an
2
Ca(OH) 2
and the union of
+ H SO = +
CaSO 4
+ 2HO
2
their anhydrides,
CaO
The nature
(cf
.
SO 3 = CaSO 4
is
of such a union
9)
:
seen from their electron formulas

!
paragraph
:O:
:O:
Ca
Charges
I
:
:6:
S:6: = Ca
:O:
:6:S:6:
:O:
+2-2
+2
~*2
The S-atom
these are furnished
80s lacks 2 electrons to complete its octet, and by sharing a pair with the O of CaO. The "acid," SOs, is an "electron acceptor," and the "base," CaO, an "electron donor." (These different systems are explained
of
becomes
three.
student who, in the meantime, at length in Chapter XXII.) skilled in using the "water system" should have little difficulty in extending his viewpoint to include the other
Exercises
1. State as briefly as possible the essential distinctions between the terms: (a) alkali and base, (&) halide and halogen, (c) concentration and amount, (d) mole and molecule, (e) noble metal and base metal, (/) electron and proton, (g) proton and neutron.
2. What is meant by each of the terms: electron, proton, kernel, nucleus, noble metal, alkali, alkaline reaction, neutralization, anhydride?
3.
Four
different atoms, A, B, C,
D, have nuclear charges

atoms.
of
6, 9, 13, 19 respectively. (a)
Give the electron groupings
in these
PROPERTIES
(b)
(c}
AND STRUCTURE
105
Which Which
of these elements are metals, and which nonmetals? of these elements will be gaseous, with diatomic
molecules, under ordinary laboratory conditions? (d) Which, if any, of the other elements will unite with
to
form an ionic compound? (e) Which, if any, of the other elements will unite with B to form a compound with electron-pair bonds? 4. Element is made up of atoms in which the nucleus contains 12 protons and 12 neutrons. What is (ci) its atomic weight, (b) its atomic number, (c) the number of valence electrons, (d) its character as a metal or a nonmetal?
5. A certain atom has 11 protons in its nucleus, (a) How many valence electrons does it have? (b) Is the solid element metallic f (c) What additional fact could be stated if the atomic weight were
also given?
6. Given that Li has 1 valence electron, Be has 2, C has 4, has 6, and F has 7, write the formula and state what kind of bonds you would expect in each of the following: (a) Li element,
element, (c) F element, (d) compound of Be and F, (e) compound of Li and O, (/) compound of Li and F, (g) compound of O
(b)
and F.
7. Which of the following reactions would you expect to take place with least evolution of heat, and which with the greatest?
+ Cl, = Ca + C1 = Cu + C1 = = Ca +
Fe
2 2
FeCl 2
CaCl 2
CuCl 2>
CaI 2
.
I2
8.
Knowing that
you expect the decomposition
zinc displaces copper from its chloride, would of ZnCl 2 or of CuCl 2 to require the
greater electrical energy? 9. Complete the following equations:
10. Determine, 2 proportion, are the anhydrides of the following substances: 3

,
+ HCl = Ba(OH) + HNO = Ba(OH) + H P0 = C H + O = CO + H O by subtracting H O in proper

Ba(OH) 2
2
3
what
2
3,
HNO H CO
Fe(OH)
8,
Fe(OH) 2
H PO HPO H PO
3
4,
8,
3,
CuOH,
106
11.
Ch.
(a) alkali, (b) acid, (c) basic
Give, by formulas, two examples of each of the following: anhydride.

radius of the
*12.
1.3
The
8
10~ cm.
How
lO" 8 cm., that of I is would this difference affect the relative heats
atom
of Cl
is 1.1
of formation of solid
Ba with
13.
gaseous
CU
BaCl 2 and BaI 2 from the reaction of metallic and 1 2? Explain.
Do you
expect
HF
or
HI
to have the larger dipole
moment?
Explain.
*
Questions of greater difficulty.
CHAPTER
VI
CONCENTRATION, ACIDIMETRY AND ALKALIMETRY

Gravimetric Analysis. The determination of the composition of any material is termed its analysis. Qualitative analysis is the determination of the kinds of matter composing the material; quantitative analysis, their amounts. The qualitative analysis of a mineral would give the information that it contains certain constituents; its quantitative analysis would yield the amount of each. Quantitative analysis may be carried out by separating each constituent from the others in a form that can be weighed this is called gravimetric analysis. For example, the amount of sulfuric acid in a solution may be determined by adding a solution of barium chloride, which produces a nearly insoluble precipitate (meaning a substance thrown down) of barium sulfate; this is filtered out on a suitable filter, dried and weighed. The amount of sulfuric acid present in the sample of solution
1.
;
analyzed can then be calculated from the relation that 98.08 g of H 2 SO 4 yields 233.45 g. of BaSO 4 2. Volumetric Analysis, There is another procedure, called volumetric analysis, where the amount of constituent is determined from the amount of a reagent (a reacting substance) necessary to complete some reaction with it, the amount of the reagent being found by having it in a solutnn of known concentration and measuring the volume of this solution necessary to .complete the reaction, a process called titration. This method is usually preferred to the gravimetric method on account of its greater rapidity. Since it is im.
portant not only for analysis but for

107
many
other purposes
108
Ch.
VI
to have clear ideas respecting concentration, we will use volumetric analysis at this point to develop them.
of an acid or alkali present in a solution is determined by volumetric analysis, since the exact usually amount of the one necessary to neutralize the other is easily determined by the aid of an indicator, a substance showing different colors in acid and alkaline solutions, which shows the end point of the titration. Suppose that we wish to detery
The amount
mine the amount

of a
of sulfuric acid in, say, 50.0 cc. can titrate it in the certain solution.
We
presence of an indicator with a solution of NaOH of known concentration, say 10.0 g. per liter, using a buret (cf. Fig. 1), a tube provided at its lower
end with a stopcock and graduated

read.
in cubic centi-
meters so that the volume of solution used can be Suppose that 20.0 cc. of the alkaline solution is necessary to neutralize the acid, as shown by the change of color of the indicator. Since 1000 cc. of the alkaline solution contain 10.0 g. of dissolved
NaOH,
0.200
g.
20.0 cc. of
it
contain 0.02
10.0 g. or
To
calculate
how much
,
sulfuric acid this
can neutralize we write the equation, 2 NaOH = 2 H 2 O + Na2 SO 4 from which, by the 2 SO 4 aid of the atomic weights, we see that 2(23.0 16.0 1.0) or 80.0 g. of NaOH can neutralize 4 X 16.0 or 98.0 g. of H 2 SO 4 Then 2.0 + 32.0 1.00 g. of NaOH can neutralize ô X 98.0 g. or
0.200 g. of NaOH, the the titration, can neutralize which is the amount in the 50.0 cc. 0.245 g. of 2 SO 4 sample of the acid solution. It is not necessary for this purpose to consider degree of ionization since all acids or bases,
F*g
1.225 g. of
SO 4 and
'
lm
Buret
amount used
in
whether highly ionized or not, must be titrated by aid of a suitable indicator to an end point where acid and base are equivalent, even though the solution is not neutral (cf Chap.
ter XIII, paragraph 30).
CONCENTRATION, ACIDIMETRY
3.
109
The amounts of acid and
alkali involved in
the neutrali-
zation are much more simply expressed if the mole is used as the unit instead of the gram. Instead of saying that 80 g.
can neutralize 98 g. of H2 SO 4 we write simply NaOH can neutralize 1 mole of H 2 SO 4 We should then express the concentration in terms of moles per liter, and 10.0 g. of NaOH per liter becomes 0.25 mole per liter since 40 g. of NaOH is 1 mole. We designate confollowcentration in terms of moles per liter by the letter the number and preceding the formula, thus 0.25 Ming NaOH means a solution containing 0.25 moles of NaOH for every liter. It should be noted carefully that it expresses a concentration of NaOH, not the quantity of it used;
of
NaOH
that 2 moles of
For example,
1 liter
2 liters
of 0.25 " "
Af-NaOH
"
contains 0.25
mole of
" "
NaOH
100
20
cc.
" "
" "
"
"
contain "
"
0.5
0.025 0.005
"
"
"
cc.
"
and so
forth, for
any volume
of solution taken.
Since solutions expand with increasing temperature, a given volume of solution will not contain exactly the same
amount
inferred
of dissolved substance
if
measured out at
different
temperatures. The magnitude
of the possible error can be
from the expansion of pure water with temperature. of 1 kg. of water is 1000.87 cc. at 15 C. and 1001.77 cc. at 20 C., a difference of approximately 1 cc. in 1000 cc. This change in temperature would therefore produce a detectible error in a titration only if the error in end point and buret readings also did not exceed 1 part per 1000, e.g., 0.05 cc. in measuring 50 cc. of solution.
The volume
It is possible, by exercising great care, to reduce the other errors to such small amounts that the fluctuations in room
temperature could interfere with a desired high degree of accuracy. Since it is usually not convenient to keep the temperature of a room sufficiently constant, the difficulty is avoided by weighing the amount of solution used instead pf
HO
measuring
its
CH.VI
weight buret, suitable for this made short in order to suspend it from an analytical balance. The concentrations of solutions to be used for this purpose are generally stated in terms of the number of moles per 1000 g. of water. Where it is desired
purpose,
is
volume.
shown
in Fig. 2. It is
to distinguish the two methods, molar concentration refers to the number of moles per 1000 cc.
of solution
and molal to the number

cc.
of moles per 1000 g. of water.
Having supposedly used 20.0

of this 0.25
in titrating the 50 cc. sample of sulfuric acid
M-NaOH
solution,
we can now say that 0.005

we
see that 2 moles of
1
,
mole of
NaOH was used. Since, from

neutralize
the equation,
mole of H 2 S0 4 evidently 0.005 mole of NaOH neutralize 0.0025 mole of H 2 SO 4 which
NaOH
the
is
If
amount present in the sample. we w;ant this amount in grams
Fig. 2.
Weight buret.
we simply take 0.0025 X 98 g. If we wish to know the molar concentration of the acid, i.e., the number of
moles per liter, we see that since 50.0 cc. of the acid solution 1000 cc. or 1 liter would concontain 0.0025 mole of 2 SO 4
tain -MHr0.0025, or 0.05 mole; hence it is 0.05 lf-H 2 S0 4 This calculation is obviously simpler than the one involving
.
grams, which necessitated the use of atomic weights. 4. The Equivalent: Normal Concentration. It is very convenient, in titration, to have various solutions of the same neutralizing power. Although it is true that solutions of such acids as HC1 and 3 of the same molar concentration may be used interchangeably in titrating bases, solu-
HNO
tions of molar HC1 and molar H 2 S0 4 for example, could not be used indiscriminately, since 1 mole of H 2 SO 4 has twice the power that 1 mole of HC1 has to neutralize alkali.
,
Similarly, while 10 cc. of 0.1
If-HCl would neutralize 10
cc.
Af-NaOH,
.
111
would neutralize only 5 cc. of 0.1 Mand bases, we are interested in the hydrogen of the acid and the hydroxyl of the base, the simplest basis for making and using such solutions is the amount of acid hydrogen and basic hydroxyl in a liter of each solution. Solutions of NaOH and Ba(OH) 2 would have the same neutralizing power if equal volumes contained, not 1 mole of each, but 1 mole and \ mole, respectively. The amount of acid and base to be dissolved in equal volumes of solution are the amounts which, in the particular reactions involved, will yield 1 g. of acid hydrogen and 17 g. of basic 1 hydroxyl, respectively. This amount is called an equivalent, and concentration expressed in equivalents is called normality in the same way that molar and denoted by the letter
of 0.1
it
Ba(OH) 2
Since, in titrating acids
concentration
is
indicated
by M. Thus
N-H 2 SO^
denotes
2 equivalents of this acid per liter; 0.5 JV-KOH denotes 0.5 equivalent of per liter. Obviously, whenever the acid
KOH
and base contain one acid hydrogen atom and one hydroxyl group in the molecule, the mole and equivalent are the same, and so molar and normal concentrations for such acids and
bases are the same.
5.
The previous example can now be

units.
reconsidered in the
of 0.25
simpler neutralized 50.0 cc. of

tration. In
We
found that 20.0
cc.
Jtf-NaOH
H S0 4
2
solution of
unknown concen-
terms of true acid and alkaline equivalence, or

it
neutralizing power,
is less
is
evident that the
H SO 4
2
solution
concentrated than the
NaOH
in the ratio 2 to 5, since
the corresponding volumes are in the ratio of 5 to 2. The concentration of the NaOH is 0.25 as well as 0.25 M,
N
.
since
mole
is 1
4
of the
liter,
H S0
2
is
equivalent in this case. The concentration therefore f X 0.25 or 0.1 equivalent per
which is written 0.1 JV-H 2 SO 4 This calculation is simpler than the one using molar concentration, as the
1 The following is a more general definition The equivalent weight for any substance for any reaction is that weight in grams which will yield 6 X 10 M unit reactions, or 1 equivalent of reaction. The unit reaction involves the making or breaking of a bond, or the participation of one elementary particle such as f he proton or electron.
:
112
Ch. VI
equation need not be used, and the concentrations can be compared instead of calculating the moles present in each volume used. It may be made to yield the same results
directly
as the other, for
equivalent of
is
H SO 4
2
is
0.5
hence a solution which

contains 4.9
6.
0.1
N-H 2 SO 4
is
0.05
mole and 49 g.; lf-H 2 S0 4 or

is
The
g. per liter. use of equivalents and normal concentration
likely to
seem more
difficult at first,
but this
is
only because
these terms are new. As soon as the initial difficulty is overcome by a little wrestling with it, these units will be found to make matters simpler. The following illustration should
TABLE
1
Ratio of base
to
acid expressed in
Base and acid
Grams
40
:
Moles
Equivalents
NaOH + HC1
36.5
KOH + HN0 2 KOH + H SO Ba(OH) + 2 HN0 3 NaOH + H3(C H O7) (citric acid)* 2 H (C H O 3 Mg(OH)
3
2
56
112
171
-f-
7)
120 123
63 98 126 192 384
1:1 1:1 2:1 1:2 3:1 3:2
1:1 1:1 2:2
2:2 3:3 6:6

acid.
Only the hydrogen atoms outside the parentheses react as
make
clear
why
this is true.
The
use of grams corresponds
to the ordinary grocery store in which a price list is required to convert pounds to cents. Using moles is like a "groceteria" in which all commodities are in packages worth $1, $2, $3,
would not need to know as much arithmetic. educated clerk could get along, however, if every package were worth just $1.00. He would be very stupid, .indeed, if he should allow himself to worry over the different sizes, weights, and shapes of the packages. Table 1 should suffice to show that the arithmetic involved becomes progressively simpler as we go from grams to moles
etc.
The
clerk
still less
to equivalents.
Summary. By way of summary it may be stated that kind of problem involved in titrating acids and bases any may be solved by understanding the three following factors
7.
10
utilizing
:
113
and
them
in
the connection
demanded by the
problem
number of equivalents and the number of grams mole of substance, as indicated by the formula; e.g., per
First, the
1 mole, 2 equivalents, 74 g. the meaning of the symbols expressing concenSecond, tration; e.g., 0.01 Af-Ca(OH) 2 denotes a solution of 0.01 mole (hence, by the first step, 0.02 equivalent or 0.74 g.)
Ca(OH) 2 denotes
of
Ca(OH) 2
in a liter.
Third, the relation between the amount of acid and base used, which is given by the equation, if amounts are expressed in moles or grams, or, if equivalents are used, 1
equivalent of any acid neutralizes 1 equivalent of any base, by the definition of the term equivalent.
8.
Examples:
What
is
(1)
the molar concentration and

of
is
(2) the normal concentration
in 2 liters of solution?
when 7.4 g. mole of Ca(OH) 2

g. is 0.1
liters,
Ca(OH) 2
are
and weighs 74
Since this
is
g.;
hence 7.4
mole and
2 equivalents, 0.2 equivalent.
dissolved in 2
1 liter
contains 0.05 mole
or 0.1 equivalent, so that the solution is 0.05 molar or 0.1 normal, expressed briefly as 0.05 Af-Ca(OH) 2 and 0.1
7V-Ca(OH) 2
9.
respectively.
40.0
of
How many cc. of 0.2 JV-HCI will be required to neutralize cc. of 0.5 N-NaOH? By 0.5 N-NaOH we mean 0.5
equivalent of
it,
NaOH
0.040
in
liter of
solution; hence 40.0 cc.
which
is
liter,
will
1
contain 0.040
0.5, or 0.02
equivalent of any acid neutralizes 1 equivalent of any base, the amount of acid neutralized by 0.02 equivalent of NaOH is 0.02 equivalent. Since 0.2 7V-HC1 means 0.2 equivalent of it per liter of solution, to get 0.02
equivalent of
NaOH.
Since
we would have to take 0.1 liter, or 100 cc. was found that the acetic acid in 10 cc. of vinegar was neutralized by 14.0 cc. of 0.5 M-K.OH solution. How many grams of acetic acid were in 100 cc. of the vinegar? The formula of acetic acid is HC 2 H 3 O 2 and only one of the hydrogen atoms in the molecule has acid properties. By 0.5 Af-KOH we mean a solution containing 0.5 mole of KOH
equivalent
10. It
,
114
liter.
Ch. VI
per
will
Since 14 cc. is 0.014 liter, this volume of solution contain 0.014 of 0.5 mole, or 0.007 mole of KOH. By
writing the equation,
KOH + HC H O = H O + KC H O
2 3 2
2,
we
see that 1
mole of the acid neutralizes
mole of the base,
so that 0.007 mole of the base will be neutralized
by 0.007
mole of the
acid,
vinegar. Since 1 weighs 0.42 g. Since this
which is the amount present in 10 cc. of mole of acetic acid weighs 60 g., 0.007 mole
amount
is
contained in 10
cc. of
vinegar, 100 cc. would contain 4.2 g. 11. If 0.654 g. of zinc is completely dissolved in 100 cc.
of 0.5
Af-H 2 SO 4 what
,
will
be the concentration of the acid
after the reaction, in terms of: (a) moles per liter, (b) equivalents per liter? The atomic weight of zinc is 65.4, so that
0.654
g. is 0.01
gram-atom
of zinc.
From
the equation for
the reaction,
Zn
+H
SO 4 = ZnSO 4
+ H2
gram-atom of zinc will use up 1 mole of acid gram-atom of zinc would use up 0.01 mole of the acid. Now 1 liter of 0.5 Af-H 2 S0 4 contains 0.5 mole and 100 cc. would contain 0.05 mole. The zinc used up 0.01 mole of this, leaving 0.04 mole of H 2 SO 4 in 100 cc., which corresponds to 0.4 mole per liter. Since 1 mole of H 2 SO 4 = 2 equivalents, 0.4 mole = 0.8 equivalent and the solution
see that
1
;
we
hence, 0.01
may
be called 0.8 normal.
from the
12. Titration Involving Other Types of Reaction. It will be seen last example above that solutions of known concentration
may
besides those where acids
be used to measure amounts of material in other reactions and bases neutralize each other. The
speed with which volumes of solutions can be measured in titrations, makes the former preferable wherever speed is desired. When neutralization of acids and bases does not take place, some other
means
Where a
may
is necessary. highly colored substance disappears in the reaction, this be used to indicate when the exact amount required has been
of indicating the end point of the reaction
added.
Any
excess
makes
itself
evident by reason of the color.
13
115
One such substance frequently used
is potassium permanganate, a substance with a deep purplish red color, which is a very KMnC>4, strong oxidizing agent. As an example of the type of reaction now being considered, let us determine how much iron is in an ore,
1.016 g. of which, when dissolved in acid so as to give a solution containing FeSO 4 required 45.0 cc. of 0.05 lf-KMnO 4 to change the FeSO 4 to Fe 2 (SO 4)3i according to the equation,
,
10
FeS0 4
+ 2 KMnO + 8 H
4
SO 4 =
Fe 2 (SO 4 ) 3
+ 2 MnSO + K SO + 8 H
4
2
0.
The
actual amount of 4 used is evidently 0.045 of 0.05 mole or 0.00225 mole. According to the equation 2 moles of 4 react with 10 moles of FeSO 4 so that 0.00225 mole of 4
,
KMnO
KMnO KMnO
would react with 5 X 0.00225 mole or 0.01125 mole of FeSO 4 Now 0.01125 mole of FeSO 4 contains 0.01125 gram-atom of iron, and since 1 gram-atom of iron is 55.8 g., 0.01125 gram-atom would
.
weigh 0.01125 X 55.8 g., or 0.626 g. Since, finally, this amount of iron was found from 1.016 g. of the ore, the iron is 61.7 per cent
of the ore.
13. Standardizing Solutions. In making solutions of known concentration for titration we must start with some substance
that can be weighed, such as benzoic acid, HCyHsC^ (only one of the hydrogen atoms has acid properties), or sodium carbonate, Na2COs. If it were desired to make 0.05 Af-H 2SO 4 which contains
,
0.05 mole or 4.9 g. of of the solution a little
about 3 cc. We would next determine accurately the concentration of acid in this solution by titrating a known weight of Na 2 COs. Suppose that it takes 43.0 cc. of our solution to react with 0.248 g. of Na2COs,
according to the equation
per liter, we would make up a quantity more concentrated than 0.05 by dissolving of concentrated acid (density 1.8) in a liter of water.
2
H SO
Na 2 CO
Since
1
+H
SO 4 =
H O + CO + Na SO
2 2 2
4.
mole of sodium carbonate reacts with
mole of the acid,
and
is
since 0.248 g. of also 0.00234 mole,
Na 2 CO
and as
is
0.00234 mole, the
amount
of
HSO*
this is dissolved in 43.0 cc. the
amount
one liter is -H^- X 0.00234 mole, or 0.0545 mole. This solution be used in titrations just as it is, or by diluting with the right amount of water the concentration may be adjusted to exactly 0.05 molal. Since 0.05 mole per liter is the same as 0.0545 mole in
in
may
116
cc., if
Ch. VI
1090
until the
resulting solution of desired concentration

process.
water is added to a liter of the 0.0545 molal solution volume becomes 1090 cc., then the concentration of the solution is 0.05 molal, as desired. From this an alkaline
may
then be
made up by a
similar
Chemists are, however, prone to take unnecessary pains to adjust their standard solutions to concentrations expressed by simple numbers. By the aid of a slide rule it is just as easy to calculate the results of titrations where the acid is 0.0545 as it is when
it is
exactly 0.05
M.
Exercises
See Appendix
II for
Answers
1. Write equations expressing the neutralization of sodium hydroxide with hydrochloric acid; sodium hydroxide with sulfuric acid; calcium hydroxide with nitric acid; barium hydroxide with
sulfuric acid.
2.
Write under each substance involved

of moles, grams,
the
number
3.
in the above equation and equivalents represented. in 1 equivalent of

3
How many
to
grams are there

of
each of the
following substances:
state
KOH, H 2SO A1(OH)

4,
From your answers

of sulfuric acid
how many grams
aluminum hydroxide and

sulfate.
will
would combine
4.
form aluminum
How many
moles of sulfuric acid
be neutralized by 4
is (a)
equivalents of sodium hydroxide? 5. If 0.98 g. of sulfuric acid is in 1 liter of solution, what the molar concentration? (b) the normal concentration?
6.
When
is (a)
what
7.
3.7 g. of calcium hydroxide are in 5 liters of solution, the molar concentration? (b) the normal concentration?
(a)
How many
equivalents of barium hydroxide are in 200

(b)
cc. of 0.1
normal solution?
How many
moles?
(c)
How many
equivalents of hydrochloric acid could this solution neutralize?
grams? a certain solution of sulfuric acid neutralized 20 cc. of a normal solution of potassium hydroxide, what was the concentration of the former in (a) equivalents per liter; (b) moles
(d)
8.
How many
If 10 cc. of
grams per liter? 25 cc. of 0.2 normal acid neutralized some base, how many 9. If equivalents of base were there? How many grams of base were there if the base was (a) sodium hydroxide; (b) calcium hydroxide?
per
liter; (c)
10. If 10 cc. of
117
N/S ammonium hydroxide
neutralizes 20 cc.
of sulfuric acid,
11.
what was the concentration

cc. of 0.2
of the latter?
How many
normal acid are necessary to neutralize
25 cc. of 0.5 normal alkali?

12.
mole of
13.
How many (a) KOH;
cc.
(b)
of 0.2
M-HC1
;
will exactly neutralize 0.02

cc. of
Ba(OH) 2
each dissolved in 500
water?
What volume
of hydrogen,
measured at 18 C. and
could be obtained by the action of zinc in excess upon

0.5
1.02 atm., 200 cc. of
Af-H 2 S0 4 ?
14.
What
is
neutralized
by 25
the equivalent weight of an acid 1.25 cc. of 0.4 W-Ba(OH) 2 ?
g.
of which
is
15. (a) How many equivalents of oxalic acid, 2 C 204, are necessary to neutralize 1 equivalent of KOH? (b) How many moles of the former for 1 mole of the latter? (c) How many grams of the
former for
16.
gram
of the latter?
11.2 liters of C1 2 at
C. and 760
if its
of
2.
The product
is
dissolved in water.
mm. react with an excess What is the molar convolume

is
centration of
17.
HC1
in this solution
final
500 cc.?
100 cc. of 0.05 Af-Ba(OH) 2 and the resulting solution is evaporated to dryness. (a) What substances are present in the residue? (6) How many moles of each? (c) How many equivalents of each?
30
cc. of 0.1
M-HC1 are mixed with
CHAPTER
VII
THERMOCHEMISTRY
1.
There are many chemical reactions
in
which our interest
lies
ordinarily not in the substances produced but in the
heat evolved or absorbed. The burning of fuel is a chemical reaction, but our purpose in burning them is not to produce the carbon dioxide and water that usually result. These
substances
and
ventilation.
we take pains to dispose of by means of chimneys Our purpose is rather to obtain the heat or
fuels, there-
light that
accompanies the reaction. In buying
fore, the important consideration is not the relative cost of the various available fuels but the relative cost of the heat ob-
therefore know how the be measured and expressed. may Again, in many reactions of importance, a knowledge of whether heat is absorbed or evolved helps to determine the most desirable conditions for carrying it out, as will be ex-
tained from each.
The chemist should
heat of such a reaction
XIV. Also in technical processes, if heat absorbed during a reaction, this may have to be considered in estimating the cost, since the heat thus absorbed may have to be supplied by means of fuel or electrical energy. 2. Heat Units. A quantity ,of heat is conveniently measured by absorbing it in a definite weight of water and measuring the rise in temperature of the water. The units chosen depend on the units of weight and temperature which are used. These heat units and the relation between them are set forth 7 in Table 1. The joule is 10 ergs, and is also a volt-coulomb,
plained in Chapter
is
that
is,
the electrical work done
when a coulomb
of electricity
flows through a resistance under a drop of potential of 1 volt, or, in equivalent terms, when a current of 1 ampere flows
for 1 second
under a 1-volt drop in potential.

118
THERMOCHEMISTRY
TABLE
1
119
Heat
Units
Amount
1 g.
of heat necessary
temperature of
to raise the
Name
calorie
Abbreviation Equivalent
cal.
1 kg.
C. at 15 C. " " C. 1 pound of water 1 F. at

1
of water 1 " "
4.185 joules
large calorie British Thermal
1000 cal. B.T.U. 1054.6 joules

kcal.
60 F.
3.
Unit
0.252 kcal.
Experimental Determination of Heats of Reaction. The of heat involved in a chemical reaction is determined in an apparatus known as a calorimeter. It consists of a vessel holding perhaps a liter of water, provided with a stirrer and a more or less delicate thermometer. This vessel must be well surrounded by some effective heat insulator, so that the temperature of the water within shall be affected only to the least pos-
amount
sible
extent by the room temperature.
This insulation may be furnished by felt, a water jacket, or, by a vacuum

jacket, as in a
Dewar
flask.
The
re-
acting substances may be introduced into the calorimeter in various ways. When the heat of solution of a solid is
to be measured, the substance
may
be
in
sealed in
a thin glass bulb immersed
water in the calorimeter. After uniform temperature has been reached the bulb is broken and the solid allowed to dissolve. If the reaction is one like the precipitation of an insoluble substance from dilute solutions, or the neutralization of an acid by a base, Bomb calorimeter. Fig. 1. one liquid may be inclosed in a thin glass vessel, or in one with a valve, and immersed in the other liquid. The liquids may then be mixed at the proper time. If the reaction is one taking place at a high temperature, it may be carried on within a "bomb" immersed in the water of the calorimeter, (Fig. 1). A small weighed portion of the material under investigation is placed within this bomb, which is then closed and filled through a tube in the top with oxygen under high pressure. It is then placed in
120
is
Ch. VII
the calorimeter and
bustion
when uniform temperature is attained the combrought about by means of an electrical connection
lid of
through the
the bomb.
The amount
of heat liberated
by the
reaction
is
measured by
the rise in temperature of the calorimeter contents and the heat capacity of the latter. If water alone were involved, the number
would be found simply by multiplying the temperature by the weight of the water. Various other substances are present, however, such as the stirrer, the containing vessel, the thermometer, etc., so that their power of absorbing heat compared with that of water must be measured or calculated " and added to the weight of the water as the "water equivalent of the calorimeter. This may be measured by allowing a reaction evolving a known amount of heat to take place in the calorimeter, or else calculated, by knowing the heat capacities or specific heats, together with the weights, of the various substances in the caloriof calories liberated
rise in
meter.
4. The amount of heat involved in a chemical reaction can be expressed by including it in the chemical equation, thus
C
indicates that
(graphite)
+ O = CO2 +
2
96,500 cal.
when
of oxygen to form 1 of heat is evolved. It
mole (12 g.) of carbon burns with 1 mole mole (44 g.) of carbon dioxide, 96,500 cal.
is now general practice, however, to express this heat as the change in heat content or "enthalpy," denoted by the symbol AH. The above process would be written
C
written
(graphite)
= C0 2 AH = -
96,500
cal.
Similarly, the formation of

2
2
NO
from
its
elements would be
N + O = 2 NO AH = +
indicating that 43,200 cal. of heat of 2 moles of NO.
is
43,200 cal.
absorbed in the synthesis
The term exothermic is often applied to reactions which evolve heat and endothermic to those which absorb heat.
be mentioned that the former predominate in reactions occurring at ordinary temperatures and the latter in those occurring at very high temperatures, in the electric furnace.
It
may
&6
THERMOCHEMISTRY
121
5. Effect of the State of the Reacting Substances. The heat of a reaction depends upon the temperature at which it is carried out and upon the state of the substances involved. For example, in the union of hydrogen and oxygen to form
water, it makes a difference whether the water produced is at a temperature at which it is liquid or vapor. Since the
of heat,
condensation of steam to liquid takes place with the evolution it is evident that where the final product is liquid
this clear
To make
follows:
when it is a gas. need to specify in the equation the state of the substance, which we would do in this case as
the heat of formation will be greater than
we
will
2H + O = 2 H O = 2HO
2
2 2
(gas)
(liq.)
+ +
115,640
cal.,
or
136,540 cal.
desirable to express the states Or, again, of all substances in the equation where ambiguity might otherwise arise, as in the equation,
find
it
we might
Hg
It
(liq.)
C1 2 (gas)
= HgCl 2
(solid)
53,300
cal.
makes a difference also whether or not a substance is solution, and what its concentration is in the solution. We might, therefore, have an equation such as the following:
in
NaOH
(0.1 molal)
HC1
2
(0.1 molal)
=
it
HO+
is
NaCl
(0.05 molal)
13,200 cal.
Where the concentration
small and does not need to be
the abbreviation, aq., specified exactly, may after the formula of the dissolved substance, which signifies
suffice to use
the presence of a large

aqiia, water.)
amount
of water.
(From the Latin
6. In a gaseous reaction in which the number of molecules of gaseous substances changes, the heat will be somewhat different if the reaction is carried out in a closed vessel so that the volume remains constant, from what it will be if the reaction is carried out so as to keep the pressure constant. Since a gas does work in ex-
panding against an external pressure, heat must be absorbed during the expansion in order to maintain the original molecular velocity
122
Ch. VII
original pressure. This behavior finds illustration in the fact that a ball thrown against a yielding surface rebounds
and hence the
with less speed than when thrown against a rigid surface. The heat of a chemical reaction at constant pressure will therefore be greater or less than that of the same reaction at constant volume according as the number of gaseous molecules decreases or increases
during the reaction.
Determination of Heats of Reaction. In many cases the heat of a reaction cannot be determined directly on account of the difficulty of carrying out the reaction in a calorimeter. In such cases it is usually possible to determine it indirectly. Moreover, even though the reactions may be easily carried out in the calorimeter, it is unnecessary to measure the heats of all, since some may be calculated from others. To do this we use a well-founded law (Hess* Law)
7. Indirect
stating that all heats of reaction depend only on the state of the initial or final substances and not upon the steps into which the reaction may be divided. This law is a consequence
more fundamental law of the conservation of energy, which states that though energy be transformed from one form to another, none of it is ever lost. The different forms of
of the
energy include heat, potential energy, or energy of position, kinetic energy, or energy of motion, electrical energy, chemical energy, etc. As an example, ZnSCX might be formed from its elements in either* of the following ways:
FIRST
WAY
+ \ O2 = ZnO S + O 2 = SO 2 SO + \ O = SO 3
Zn
2 2
ZnO
Total:
Zn
+ SO = + 2O =
3
2
ZnS0 4
ZnSO*
AH AH AH AH AH
=====-
85 kcal.
70 kcal.
22 kcal.
53 kcal.
230 kcal.
WAY = ZnS Zn + S AH = = ZnSO4 AH - ZnS + 2 O 2 Total: Zn + S + 2 O 2 = ZnSO4 -AH - SECOND
40 kcal.
190 kcal. 230 kcal.
THERMOCHEMISTRY
total result in either case
S,
123
The
is the formation of ZnSO4 with the evolution of heat. Our law tells us that the total heat liberated is the same in either case, as shown by the above figures. As a consequence of this, thermochemical equations may
from Zn,
and
O2
be added or subtracted
like any algebraic equations. Suppose that the following heats of reaction have been measured:
and
2
AH = C + O 2 = C0 2 CO + O 2 = 2 CO 2 AH = 2
96.5 kcal.,
(1) (2)
135.0 kcal.,
:
and we wish to learn the heat
of the reaction
2
O2 =
CO.
All that
tions.
is necessary is to eliminate CO 2 from this pair of equaWe may double equation (1), if we at the same time multiply by 2 its value of AH 2 C + 2 O 2 = 2 CO 2 AH = - 193.0 kcal.
:
we may we change the

Also,
2
write equation (2) in the reverse direction, sign of its value of AH

:
if
C0 2 =
2
CO + O2 AH = +
2
135.0 kcal.
Addition of these two equations gives us the reaction
we
desire :
CO AH = - 58 kcal. If, on the other hand, we eliminate O from the pair of equaC
+O
tions (1)
and
(2),
we
obtain the equation for a different reaction,

2
+ CO
CO AH = +
38.5 kcal.
2 O 2 aq. from its Again, it is not possible to synthesize elements in the calorimeter, but the heat that would be evolved if the reaction were possible may be calculated from the fol-
lowing:
H O aq. = H O + % O + H +\O = HO
2
aq.
AH = AH = -
23.0 kcal.,
68.4 kcal.
Subtracting the
tain:
first
from the second to eliminate
HO
2
we
ob-
H +
2
aq.
= H 2O 2 aq. AH = -
45.4 kcal.
124
Ch. VII
From this we learn that H2O2 is an exothermic compound, formed from its elements with the evolution of heat. 8. Fuel Value of Foods. The heat and muscular energy needed by the body are furnished by the oxidation of food
materials.
The metabolic
oxidation of sucrose (a typical car-
bohydrate), stearin (a typical fat), and a typical protein can be represented by the following equations
:
iV Ci 2 H 2 2On
yihr c 5 7H 110 06 0.213 (C 4 .3H 7 6 ON)
.
+ + +
H 2 O, O 2 = CO 2 + o2 = H 2o, co 2 + O 2 = 0.809 CO 2 + 0.1063 CO(NH 2
)2
+
sucrose
is
0.595
2 O.
Per mole of oxygen, the heat liberated by the metabolism of

112.47 kcal., of stearin 110.86, of the protein 97.88,
diet including carbohydrates, fats,
and of an average
teins 108.1.
and pro-
The amount
of food energy needed
by a person
varies accord-
ing to his weight and the amount of his muscular activity. In this country, the daily per capita consumption of food proM vides about 3000 kcal. The "starvation level is somewhat
lower than 2000 kcal. per day. A knowledge of the fuel value of various foods is useful, for example, in nutritional research, or in determining the least
weight of food necessary for a camping or exploring expedition. It may be of interest to have the few figures given in the following table:
Foods
Approximate number kcal. per pound

etc.
Starchy foods, cereals, flour, rice, beans, Sugar Fats and oils Cheese Chocolate Milk, evaporated, unsweetened Milk, condensed, sweetened Dried fruit Fish
Meat
1650 1860 3650 2000 2850 800 1500 1300 1000 1600
Of
course,
wholesome, well-balanced
other considerations must also enter to secure a diet, but these canno't be discussed here.
THERMOCHEMISTRY
Exercises
12*
See Appendix II for Answers

1.
What
is
the distinction between heat and temperature?
2. Calculate the
heat of the reaction

2
CaO
+ CO = CaCO
2
from the following:
CO 2 + Ca(OH) = CaCO + H 2O AH = CaO + H O = Ca(OH) AH = 3 2 2
30.5 kcal. 11.5 kcal.
3.
Calculate the heat of the reaction
Zn
+
+
C1 2
aq.
ZnCl 2 aq.
from the following determinations:
Zn
HC1
2
aq.
H +
C1 2
aq.
HC1
4.
(gas)
= ZnCl aq. + H = 2 HC1 (gas) = HC1 aq.

2
AH = AH = AH = :
36 kcal. 44 kcal.
17 kcal.
(a)
Calculate the heat of the reaction
N + 3H =
2
NH
2
from the following:

4
NH + 3 O = 2 N + 6 H O H + | O = H O (liq.)
3
(liq,)
AH = AH = -
364 kcal.
68.3 kcal.
(6)
The above
Given that
of formation of
5.
NH
figures are for constant pressure;

3
be greater or
less at
would the heat constant volume?
C O 2 = CO 2 96.5 kcal., and that anthracite considered as 95 per cent carbon, costs $10 per ton (= 1000 coal, kg.), determine the cost of 1000 kcal. from the burning of this coal,
6.
indicated
Considering "water gas" to consist of by the equation of its formation,
CO
and
only, as
C+H
and given the heats
of
= CO + H
2,
CO and H i.e., = CO 2 AH = - 68.0 kcal. CO + | O 2 H 2 + O = H O AH = - 68.3 kcal.

combustion of
2, 2
2
calculate the cost of 1000 kcal. from this gas if it costs 90f per 1000 cu. ft. ( = 28,300 liters) when measured at 20 C. and 1 atm.
pressure.
126
Ch. VII
7. If kerosene were pure Ci H22, whose heat of combustion is 1626 kcal., and costs ISff per gallon (3.781 liters) and has a density of 0.79 g. per cc., calculate the cost of 1000 kcal. obtained by burn-
ing kerosene.
" "grub-list for two men on a ten-day walking tour, endeavoring to get the minimum weight consistent with variety and palatability.
8.
From
the table on page 124
make out a
CHAPTER
VIII
ELECTROLYTIC DISSOCIATION
Such a large proportion of the reactions with which concern ourselves take place in water solution that the behavior of substances dissolved in water is a subject of great importance. We will consider a number of the properties and reactions of substances in aqueous solution, and see that conclusions that may be drawn as to the nature of these solutions are in agreement with the picture in Chapter V. 2. Solvents for Different Types of Solids. We can better understand the nature of aqueous solutions if we first consider the process of solution in general. In relation to the different
1.
we
types of solids outlined in Chapter V, paragraph 15, a solid composed of distinct molecules is best dissolved by a liquid whose intermolecular forces are of approximately the same strength and nature as those existing in the solid. For example, solid sulfur, containing molecules of Sg, is readily
dissolved
Naphthalene, Ci H 8 is readily dissolved by hexane, CeH^. Water is a very poor solvent for these substances because the field of force around a water molecule is different from the fields of force surrounding the molecules just mentioned. The electrons are much more the property of the oxygen than of the hydrogen, hence the water molecule is relatively positive in one part and negative in another. Such a molecule is called an electric dipole (cf. Chapter V) and is surrounded by an electrostatic field, very different in nature from the field of force surrounding a sulfur molecule. Water is, however, a good solvent for a substance like sugar, whose molecules contain a number of OH groups, each an electric dipole similar to the water dipole. Solids
by
liquid
CS2
of the
diamond type are usually nearly insoluble in

127
all
solvents.
128
Ch. VIII
Solids of the salt type are not dissolved by liquids whose molecules are surrounded by symmetrical fields of force such as benzene or gasoline but they are dissolved by liquids
whose molecules contain electrostatic dipoles, including water, liquid ammonia, and a few others. The process of solution in such a case is easily pictured (Fig. 1). When the water
molecule reaches the surface of a salt crystal
it
tends to
)(
'
Solid
Water
solution
Fig. 1.
The
process of solution of a salt in water.
orient with its negative part towards the positive potassium atom and its positive part towards the negative chlorine
of the crystal so that,
atom. This weakens the force between the charged atoms if it is not too strong, the charged atoms may be detached from the crystal and wander off into solution each surrounded by an envelope of oriented water molecules. These charged* atoms in solution are but weakly attracted to each other and can move about in the
solution
more or
less
independently.
They
are accordingly
called ions,
from the Greek word meaning to wander. We will now examine certain properties of salt solutions to see how they harmonize with this conception regarding
their nature.
3. Abnormally Great Lowering of the Freezing Point. It has been pointed out in Chapter III that the molecular weight of substances may be determined by two essentially identical methods. Both methods depend upon the fact that
$3
129
a standard number of molecules (6 X 10 23 or 1 mole) produce certain effects which are independent of the mass, structure,
or identity of the molecules. 23 Thus, 1 mole of any gas (6 X 10 molecules) occupies 22.4 1. at C. and 1 atm. Again, 1 mole of any soluble substance produces the same effect, in general, as 1 mole of any other substance with respect to lowering the freezing point, or raising the boiling point of water solutions. It is even possible as an alternative to define a mole from the empirical viewpoint as the number of grams which in the gaseous state at C. and 1 atm. will occupy 22.4 1., or else as the number of grams which, dissolved in 1000 g. of water, will lower the freezing point of the solution 1.86 C.
below that of pure water. If we determine the effect of various substances in lowering the freezing point of water, we find that a large number of them show concordant behavior.
Other substances, including abnormally great lowering
acids, bases,
and
salts,
show an
This
is
of the
freezing point.
illustrated in the following table:

TABLE
1
Substance
Freezing points of 0.1 molal solutions, C,
Sugar
Glycerine Alcohol
NaCl HC1
KNO
BaCl 2
Na 2 SO4
- 0.188 - 0.186 - 0.184 - 0.348 - 0.356 - 0.330 - 0.478 - 0.459
It will be seen that the first three substances in the table behave as would be expected, but that the others give an abnormally great lowering of the freezing point. There are
two ways
of accounting for this abnormality.
Either the
law of the uniform molal lowering does not hold universally, or else acids, bases, and salts dissociate into two or more independent parts when dissolved in water. If this law still
130 holds, then 1
,
Ch. VIA
mole of NaCl, HC1, or KNO3 when dissolved a large quantity of water, seems to yield nearly 2 moles of dissolved substances, whereas 1 mole of BaCl 2 or of Na2SC>4, seems to yield nearly 3 moles of dissolved substances. These results harmonize perfectly with the picture of such solutions given above according to which 1 mole of KC1 in solution exists as 1 gram-ion of K+ and 1 gram-ion of Cl~, nearly independent of each other, and each exerting its effect upon the freezing point. This effect is proportional
in
,
chiefly to the total concentration of ions or molecules in solution and is scarcely influenced by their nature, size, or
charge.
4.
Thus
0.1
mole of Br2
CH 3OH,
Na+, Cl~, and
SO 4
would each
The
affect the freezing point to the same extent. theory that acids, alkalis, and salts may be dis-
sociated into charged ions was advanced by Arrhenius in 1881, long before it had been shown that the solid salts also
contain charged atoms, and it seemed absurd to many to think of sodium chloride dissolving as atoms of sodium and chlorine, sodium being a metal that reacts violently with water and chlorine a poisonous gas. Such a difficulty is avoided
by realizing that an uncharged atom and a charged ion are quite different substances. Thus Cu is copper, a reddish metal Cu++ or cupric ion, existing in water as a greenish blue sub;
very different from Cu in all its properties. Again, light, combustible gas, while H+ is a substance existing in solution, along with some negative partner, and having a
stance,
is
2 is
sour taste, etc.

5. Independent Migration of Ions in Electrolysis. It has been found that all dissolved substances that give the abnormal effect on the freezing point of water also give solutions which conduct the electric current, depositing materials at the electrodes, or else dissolving the electrodes. Because
of this behavior they are called electrolytes. Those conducting very well, the strong acids and alkalis, and most salts, are
called strong electrolytes.
This conductivity is quite in accord with the presence in the solution of charged ions, which must necessarily migrate
6.
131
towards an electrode of opposite charge when voltage is applied. The negative electrode, called the cathode, the one which is receiving electrons from the dynamo or battery, attracts the positive ions, which are accordingly called
cations, while the positive electrode, the anode, attracts the negative ions, called anions. It is possible to detect this
migration experimentally. If, for example, we have a Utube containing, say, dilute copper sulfate in the bottom, with dilute potassium nitrate _ A
,
carefully superimposed as shown in Fig. 2a, and allow
an electric current to pass through the solution for a

time, we will find that the blue color characteristic of
copper salts travels towards

the negative pole, while the sulfate ion travels towards the positive pole, as might be
shown by
barium
testing layers of solution with a solution of

chloride.
The
state of
Fig. 2.
Independent migration of the

ions in
electrolysis. passage of a current is depicted in the figure at 6. Whenever electrolysis takes place it is possible to show such independent migration of the two parts of the salt, acid, or base, by appropriate
affairs after the
experiments similar to the above. 7. Discharge of the Ions at the Electrodes. Since in electrolysis it is observed that current continues to flow so long as sufficient voltage is applied and there are ions in the solution, it is obvious that electrons must be able to pass
from the solution to the wire, or external circuit, and vice The pole at which the electrons enter the solution is called the cathode or reducing electrode; conversely, the pole at which they leave the solution is called the anode or oxidizing electrode. (Note that anode and oxidation begin with vowels, cathode and reduction begin with consonants.)
versa.
132
If
we
represent an electron
Ch. Vlli
by the symbol,
charge of ions at a cathode such as the following

:
may
e~, the disbe represented by equations
H+
Ag+ Cu++ +
In
+ e~ = + e~ =
2 e~
H, followed by Ag; Cu.
H = H2
some cases an
without
1
ion
charge
To
deposit
"^ eT = Fe++. deposited, as Feof an element whose ion has 1 gram-atom

being
1
may
be reduced to an ion of lower
10 positive charge, such as Ag+ or H+, requires 6.0234 electrons (cf. Chapter V), 1 equivalent of electricity; twice
as much, or 2 equivalents for ions with 2 positive charges, such as Cu++ or Zn++, and so on. The quantity of electricity 23 electrons, the electrochemical represented by 6.023 X 10
is obviously very important and is called one faraday, in honor of Michael Faraday, who discovered the laws of electrolysis. Its magnitude in practical units is 96,500
23
equivalent,
1 coulombs, a number worth remembering. At the anode, where electrons leave the solution, we may have reactions such as Cl~ = Cl e~, followed by 2 Cl = C1 2 . Frequently the electrons may come from some source other than the anions in solution. Thus, if the anode were made of copper, the electrons removed from the anode would come not from CP in solution but from atoms of copper going into solution as Cu++. Again, when SO 4 is present, although it carries part of the current to the anode it is the water, not the SO 4 which eventually gives up electrons to the anode;
H+ + | O2 + 2 e". (It ~~~~ = SO 3 + \ O 2 is SO 4 reaction = 2 H+ + SO 4~~~~. The sum H2 O

2
H2O =
is
sometimes said that the

2 e~, followed
by SO 3
of these
two
is
the reaction
There
1
previously written, which is the final result in either case. is probably no evidence that electrons are any more
1 A coulomb is the amount of electricity carried by a current of 1 ampere in second; e.g., 10 amperes flowing for 1 minute would amount to 600 coulombs, and if 1000 coulombs are delivered in 50 seconds, the current strength is 20 amperes. Practically it is defined as the amount of electricity that will deposit
0.001,118
g. of silver.
$10
removed from 864
than from
133
easily
is all
1
H O, and the
2
net result
are sure of.) In any case Faraday's Law holds, and faraday of electricity releases J CU, \ 62, etc., or dissolves
we
i Cu++, etc.
following further examples may serve to make the matter clearer. Since 108 g. of silver is 1 gram-atom, deposited by 96,500 coulombs, to deposit 1 g. would require yj-g- of
8.
The
96,500 coulombs, and to deposit 5 g. would require Y^-g- of 96,500 coulombs, or 4470 coulombs. If this were done by a current of 2 amperes (2 coulombs per second), the time
required would be 2235 seconds, or 37 minutes, 15 seconds. However, to deposit 63.6 g. of copper, from ordinary copper
salts, 65.4 g. of zinc, etc., requires
twice as
much
electricity,
or 2 faradays. Similarly, certain other ions require 3 faradays
per gram-ion.
9. It is worth noting that the fact that whole numbers of faradays are required to discharge 1 gram-atom of different elements implies that 1 or more elementary electric charges are involved in changing
atomic
railed.
ions to atoms, or, in other words, that electricity, like matter, is in structure, not a continuous "fluid," as it was once often
The experimental
facts
constitute,
1 '
"definite
and simple multiple proportions
essentially, laws of for electricity as for
other forms of matter.

10.
Formulas of Ions. The formulas of ions are simply
related, in
many
cases, to the
free
number
of outer or valence
electrons
atom, which, in turn, is correlated with the group of the Periodic System to which an element belongs (cf. Chapter XVII). Thus, the hydrogen atom has one electron and gives H+, the calcium atom has two electrons and gives Ca^*, etc. The student should learn the formulas of the common ions, such as Na+, K+, Ag+, Cu**, Zn^, Ba++, A1+++, Fe++ and Fe+++, OH", Cl~, Br~, NO3~, SO 4 and CO3 When the formula of one ion is known, that of its accompanying ion can be derived; for example, it is obvious that knowing that Th (864)2 must give SO* H~H~. Similarly, the formulas of solids or thorium ion is Th"
.
,
upon the
134
Ch. VIII
undissociated molecules follow from the ionic charges, such = A1 2 (SO 4 ) 3 4 K+ 3 S0 4 as 2 A1+++ Fe(CN) 6 "" = Ca(H 2 PO 4 ) 2 Ca++ 2 Ca++ 2 PO 4 4 Fe(CN) 6
HPO 4" = CaHPO 4

;
+
;
Ca++
POr
= Ca3 (PO 4 ) 2
properties of dilute aqueous solutions of strong electrolytes are the sum of independent sets of properties,
11.
The
hence independent substances are present. The properties

of solids cannot be simply referred to the properties of their constituent ions, since these ions, in crystals, are so close together as to modify each other's properties. Solid CuCl2 ,
CuBr2 and Cu(NO 3 ) 2

,
2 O,
for example, are colored green,
brown, and blue, respectively. The copper ions are the source of color but their color is modified differently by each different
or, in the Cu(NO 3 ) 2 the water surrounding the Cu++. All three salts, by however, give the same blue color when dissolved in dilute " water solution, indicating the presence of the same Cu" aq.
species of adjacent colorless ions,
H 2O,
"
each case. The ions are influenced now mainly by the water molecules surrounding them; the different ions are too far apart to have more than slight effect upon each other. The
in
therefore, the
properties of a dilute solution of a strong electrolyte are, sum of the properties of the water and of the
all
constituent hydrated ions. This applies to

electric
properties, including density, conductivity, color, refractive index, and chemical behavior. It makes no difference, for example, whether we make a solution by dissolving 0.1 mole
KNO 3 or by dissolving 0.1 mole each of and KC1, the result in either case is a solution containing 0.1 mole each of Na+, K+, CP, and NO 3 ~. The conductivities of these four salts at 25 C. in 0.1 molaf solution are given in Table 2. We see that there is scarcely any difference between the sums corresponding to the presence of equal amounts of the same four ions. Obviously the conductivity of any one of these solutions could be calculated with good accuracy from measurements on the other three.
each of NaCl and
NaNO3
Most
It is
perhaps, are the chemical reactions* not possible to predict the properties of gaseous HCI
striking of
all,
11
135
from the properties of hydrogen and those of chlorine, but it is possible to predict the properties of a dilute aqueous solution of HC1 from the properties common to all other acids, on the one hand, and those common to all soluble chlorides on the other hand. The hydrogen ion in this solution reacts in the same way and has the same properties as the hydrogen ion obtained from any other acid, as explained in Chapter V. It affects indicators in the same way, it reacts
TABLE 2
Conductivities of 0.1
Molor
Solutions at
25 C.
0.00987 0.01286
0.02273*
NaCl
KN0
0.01066 0.01201
0.02267
NaNO3
KG
Sum
Sum
with carbonates, dissolves zinc, tastes sour, just as it always does unless the other ion present exerts some complicating effect on these tests. The chloride ion gives precipitates with the same reagents, such as AgNO 3 or Hg2 (NO 3 ) 2 solutions, as are obtained from all other chloride electrolytes. Knowing the properties of chloride ion, as obtained from some chloride, and knowing the properties of a cation, say barium ion, we can predict the properties of dilute solutions of barium chloride, without the aid of direct experiment. This makes it
possible to simplify enormously the labor of learning the chemical reactions of electrolytes upon each other. It is necessary only to know the reactions given by the important ions in order to predict the reactions of the enormous number of electrolytes which might be obtained by combinations of these ions. Instead of remembering the action of a large
number
of sulfates individually
it suffices to
upon all soluble barium salts, remember that barium ion, Ba^*, reacts with
,
sulfate ion,
SO 4
to give a very insoluble white precipitate
of barium sulfate,
made with any
generalizations cannot be of assurance with substances that are degree

.
BaSO 4 Such
un-ionized. Alcohol and phenol (carbolic acid) both contain the hydroxyl group (OH), their formulas being C2H 5 and C0H 5OH, respectively, but these are not appreciably ionized,
OH
136
in
Ch. VIII
and when dissolved no set of properties
water react very
differently,
it is
having
in
common. Again,
,
not correct to
conclude that silver nitrate is a "test for chlorine/' as is sometimes stated. Chloroform, CHC1 3 will give no such test unless it is heated with silver nitrate for a long time. A solution of potassium chlorate gives no precipitate with
silver ion,
Ag+, because, although

ion,
it
contains chlorine,
it
yields
no chloride
CP,
but, instead, chlorate ion,
C1O3".
of the ionic theory is very great in reducing equations to their simplest terms and focusing the attention on the essential reactions taking place.
The value
Heats of reaction in dilute solutions of strong electrolytes depend on the reacting ions only. Heats of reaction between ions in dilute solution are independent of the nature of any other ions present. This is not true for substances not in solution. Solid NaOH and solid KOH do not give the same heat of neutralization with concentrated hydrochloric or nitric acid, but when both acid and base are dilute, the
12.
is always the same, 13,700 calories Since the heat liberated is the same, the per equivalent. reaction liberating it is likely to be the same, and the ionic
amount
of heat liberated
theory indicates that this should be the case. Instead of

writing
NaOH + HC1 = H 2 + NaCl

and
KOH + HN0
+ KN0
we
for the reactions in dilute solution,
which would lead us to

should, according to
expect different heats of reaction,

previous evidence, write Na + OH- H+ Cl-
AH =3
Na+
Cl~
13,700cal.
K+
The
+ OH- + H+ + N0
ionic
AH =-
= H 2O
+ K+ + NO ~
3
13,700 cal.
to anything except
form of the equations indicates that nothing happens H+ and OH~ which unite to form H 2O;
13
13T
the other ions, being unaffected, tion, leaving simply
may be canceled from the equa13,700 cal.
H+
+ OH- = H O AH = 2
as the fundamental and only reaction in both cases. The same would apply to precipitations. Any soluble barium salt would give the same heat effect per mole with any soluble
sulfate, since,
no matter what other ions are present

is
in the
solution, the essential reaction
Ba++
SO 4
= BaSO 4 AH = -5600
cal.
2 SO4 solutions be used, the heat If, however, Ba(OH) 2 and of reaction would, of course, be no longer the same as above, for then we would have occurring simultaneously two inde-
pendent reactions, each with equation
its
own
heat
effect,
and the
ionic
Ra++
+ 2 OH- + 2 H+ + SO ~ =
4
BaSO 4
+ 2HO
2
AH =
X (-
13,700)
5600
cal.
shows that nothing should be canceled
out.
13. Degree of lonization of Strong Electrolytes. In very dilute solutions, the ions of strong electrolytes are so far apart as to be without influence on each other, but as concentration increases,
electrostatic
attractions and repulsions come into play, each positive ion tending to surround itself with negative ions, and vice versa. This attraction restricts their independence and prevents
them from
exerting their full individual effects. For example, they
suffer a drag as they move in opposite directions while conducting an electric current, as shown in Table 3, which gives the current
electrodes
that would be carried by a mole of KC1 at 18 C. between parallel 1 cm. apart when diluted by different volumes of water. The limiting conductivity in very dilute solution is evidently about 128, but this is greatly reduced as higher concentrations are reached.
The
on the freezing point is likewise additive only at low concentrations. If a salt gives two ions, the ratio extremely of the freezing point lowering to the concentration should be 2 X 1.86 = 3.72 (cf. paragraph 3). This is closely approached by 0.001 M-KCl, as seen in Table 3 on page 138, but becomes less
effect of ions
at higher concentrations.
138
Ch. VIM
There are other factors that may contribute to these deviations beside the one mentioned above. One of these may be the repulsions suffered by the ions when they happen to come very close to each
may be their varying degrees of hydra tion. In many a given pair of ions may temporarily unite to form a cases, also, molecule. This union is strong in the case of the weak acids and
other; another
TABLE
3
Effects of Ionic Interaction for
KCI
Concentration moles 1000 g. of water
per
0.0002
0.001
127.1
0.01
0.1
Conductivity
divided concentration
by
127.9
122.2
3.61
113.7
3.45
98.1
3.25
Freezing point lowering divided by concentration
3.65
bases and a few
salts,
Even such a strong
and is appreciable in the case of many salts. acid as nitric shows evidence of the presence of
HNO
molecules in concentrated solutions.
The weak
salts
men-
tioned below, in paragraph 15, represent cases of incomplete dissociation. In some cases intermediate ions are formed, as Pb++
OP =
Cl" = PbCl 3~~. PbCl+, and PbCl 2 The various formulas connecting the concentrations of the ions
with the properties of their solutions all require modification to take into account the several kinds of interaction. Students who
pursue this subject further into the realm of quantitative relationships will encounter factors called activity coefficients, which correct the ionic concentrations so as to allow for the variations
here discussed. However, the qualitative reasoning called for in this book will yield sufficiently accurate results if we treat strong acids and bases and nearly all salts as completely ionized, the ions
having effects proportional to their concentration.
should be understood that the omission from an equation of ions which are unaffected by the reaction does not imply that they can be absent from the solution. Although the
It
OHT = 2 O represents the only chemical equation H+ that occurs in the neutralization of solutions of strong change acids with strong bases, the solutions mixed must contain
other ions;
it is
impossible to
make one
solution containing
14
139
H+ and another containing only OH~; some ion of opposite charge must be present in each, but it makes practically no difference whether the ion associated with H+ is
only
Cr, NOs",
OH"
is
ClO 4 ~, nor whether the ion associated with Na+, K+, Rb+, or Cs+. The fact that some other ion
or
in the solution is
if
no reason for putting it into the nothing happens to it. Indeed, one cannot have these solutions without vessels to hold them, test tubes, or beakers, or flasks, or some other, but that fact is no reason for adding test tubes to both sides of an equation. A chemical equation should show only the chemical changes, and not be overburdened by the formulas of molecular species which are not reacting. 14. Weak acids and bases are less ionized than strong acids and bases in solutions of the same concentration. There are some acids and bases which show the properties
equation
of hydrogen and hydroxide ions, respectively, to a much less extent than do strong acids and bases in solutions of
must be
the same concentration. Solutions of HC1, 3 and H 2 SO 4 the same concentration, say 0.01 normal, would have at about the same sour taste, but 0.01 normal acetic acid, HC2H 3O2, would not taste nearly so sour. The first three acids would show almost identical colors with an indicator like methyl violet, sensitive to that degree of acidity, but
, ,
HNO
it
the same color.
would require approximately normal acetic acid to show The same weakness on the part of acetic acid is shown in power to conduct current. While, therefore,
the properties of acetic acid indicate that it yields hydrogen ion in water, they also indicate that only a little of the hydrogen of the acid is ionized. Again, while the effect of acetic acid on the freezing point of water is greater than that of an un-ionized substance like sugar, it is not double the latter, as is approximately the case with an acid like hydrochloric acid. Its heat of neutralization is no longer 13,700 cal., as with a strong acid, but has a different value, 13,400 cal., which includes the heat of dissociation of the acid during
its neutralization.
140
Ch.VTO
There are a number of such weak

acid,
acids, including carbonic
H BO3 hydrogen sulfide (hydrosulfuric acid), H 2 S, silicic acid, H Si03 (also many polysilicic arsenous acid, H AsO arsenic acids), nitrous acid, HNO and hydrocyanic acid, acid, H As(>4, sulfurous acid, H SO H C03
2
,
boric acid,
2,
3,
3,
HCN,
hypochlorous acid, HC1O,

TABLE 4
etc.
Table 4 gives the con*
Approximate Concentration of
H + in Solutions of Various Acids

1
1
Moles of Acid Dissolved per Liter
0.1
0.0 1
Hydrochloric
Nitric
Bisulfate ion
HC1
0.1 0.1
0.01 0.01
HNO
(NaHS0 4
Acetic
soln.)
Carbonic
Hydrosulfuric
HSOr HC2 H O2 H CO3 (CO*

3
2
0.2
0.004
in water)
0.04 0.0013 0.0002
HS
2
0.0001
O.OOa 0.0004 0.00006 0.00003
centration of
H+
in solutions of four
weak
acids
compared
with two strong acids, and indicates clearly the different extent of the ionization. The degree of ionization is the
fraction, or per cent of the total electrolyte present, which has broken down into ions. For example, the figures for
if 0.1 mole of acetic acid is dissolved mole of H+ is liberated; since every H + produced requires one molecule of HC 2 HaO2 to split up, 0,0013 moles of the acid have dissociated, which is 0.0013
acetic acid
show that
in 1 liter, 0.0013
or 1.3 per cent of the acid taken. It is to be noted that as a weak acid is diluted the degree of ionization increases although the concentration of H+ diminishes.
4- 0.1
is
The most important weak base ordinarily encountered ammonium hydroxide, NH 4 OH. It is this weakness which
it
makes
enough
if
useful in cleansing, for although it does not yield free hydroxide ion to be injurious in washing, yet,
the little it does yield is used up, more can dissociate, the undissociated portion acting as a sort of reserve for hydroxide
15.
ion.
Weak
Salts.
Most
salts are highly ionized

salts of
when
in
solution,
even though they be
weak
acids or bases,
17
like
sodium acetate or ammonium
chloride.
141
There
is,
however,
a great range in the degree of ionization of

including lead acetate,
Pb(C 2 H 3O 2 )2,
,
and some, cadmium iodide, CdI 2

salts,
,
mercuric chloride, HgCl 2 and mercuric cyanide, Hg(CN) 2 are very weak. These salts are poor electrolytes, and their
show the presence of relatively few ions. ordinary soluble chlorides give a precipitate of lead chloride, PbCl 2 on the addition of lead ion to their solutions. With mercuric chloride, however, no precipitate is obtained, indicating that there is less chloride ion in a concenreactions in solution
For example,
all
trated
solution
of
mercuric chloride
than
in
a saturated
If,
solution of the rather insoluble lead chloride.

silver ion is taken,
AgCl,
is
much
less
however, a precipitate is formed, for silver chloride, soluble than lead chloride, and HgCl 2 yields
it.
enough chloride ion to precipitate

16. Ionization of
found that the

of a polybasic dissociate with
hydrogen atom
to neutralize
it
Polybasic Acids in Steps. It is two or more hydrogen atoms in the molecule acid, like H 2 CO 3 H 2 S, or H 3 PO 4 tend to unequal readiness into ions. While the first of H 2 CO 3 is but sightly ionized, it is possible
, ,
Weak
with
OH
",
forming water and
HCO3
~",
before
the neutralization of the second hydrogen atom, in the 3 ~, begins. This explains the ease with which it is possible to form acid salts in such cases. The first atom of hydro-
HCO
3 PO 4 ionizes readily, corresponding to a moderately gen in ~ with much less 2 PO 4 strong acid; the second ionizes from ~ is a rather weak acid, while the ease, so that the ion 2 PO 4 third is hard to neutralize, HPO 4 being a very weak acid.
Conversely,
when hydrogen
,
ion,
H+,
is
added to an ion
like
it is taken up very completely at first until the latter ~ then less completely until H 2 PO 4 converted into HPO 4 is formed, and then only a little to form H 3 PO 4 Similarly, the first step is the formation of when H+ is added to CO 3 HCO3~, the second is the formation of H 2 CO 3 or CO 2 Even
PO 4
is
H SO 4
2
forms some
HSO 4
"
in
more concentrated
solutions.
17. Ionization in
the chief solvent in
Other Solvents Than Water. Water is which we are interested, but there are
142
Ch. VIII
others which can dissolve electrolytes with ionization. The most important of these are liquid ammonia and the alcohols.
Ionization in
is less
all other solvents that have been investigated than in water, and seems to be roughly proportional
to the dielectric constant of the liquid. The following values for the dielectric constants for several liquids are of interest in this connection
:
Water Methyl (wood)

Ethyl alcohol Acetone
80
alcohol
Ammonia
Chloroform Ether
16
5
31
26
22
18. Ionization of
Fused
Salts.
Fused
salts
appear to be highly
ionized, conducting the electric current very readily. This corresponds to the fact that melting a salt like NaCl merely releases
the charged atoms, Na+ and CP, already present, held in fixed positions in the solid state, but free to move in the molten state
On account of this high conductivity substances are obtained industrially by the electrolysis of fused salts rather than of aqueous solutions. This is the case especially with metals such as sodium, calcium, and aluminum, where, instead of the desired metal, the hydrogen from the water would be
towards charged electrodes.
many
deposited at the cathode. Sodium and calcium are obtained, along with chlorine gas, by the electrolysis of their fused chlorides. Aluminum is obtained by the electrolysis of A1 2O 3 dissolved in fused
cryolite,
Na AlF
3
6.
of Water. Water itself is very slightly The purest water that can be prepared has a very + slight conductivity due to H and OH~. Knowing the conductivities of these ions in more concentrated solution, as
19. Ionization
ionized.
we do from measurements
with acids and bases,
it is
possible
to calculate the concentration of these ions in water to be 1 7 approximately 10~ molar at ordinary temperatures. This corresponds to 0.1 milligram of H+ and 1.7 milligrams of
OH"
1
per ton of water. Other methods of measurement confirm these figures.

This number
is
equivalent to writing
107
or
10.000.000
20
20.
The method
of calculation
143
is illustrated
from conductivity
by
the following scheme.

Solution
measured
0.001
Ions present
0.001
Conductivity at 18
C*
M-HC1
0.001 Jkf-KOH
0.001
M-H+ + M-K+ +
0.001 0.001
M-CF M-OH"
Sum
377 234
611
127
0.001
M-KCl
0.001
0.001
if
M-K+ + 0.001 Af-CF M-H+ + 0.001 M-OIT
484
X X X X X
1<T
IP" 6
10-*
1<T
they could exist together
Pure water
Conductivity
is
x molal
H+ + OH~
0.042
1CT 6
proportional to concentration, therefore
Exercises
See Appendix
1.
II for
answers
terms of the ionic
How
would you define
acid, base, salt, in
theory?
2.
Summarize
in writing the evidence in favor of the theory
of electrolytic dissociation.
3. State in writing all the evidence you have learned, showing that a solution of acetic acid is much less ionized than one of hydrochloric acid of the same concentration.
4.
Divide the following substances into two
lists,
one for those
slightly ionized in water, the other for those highly ionized: ammonium hydroxide, ammonium chloride, hydrochloric acid, sodium acetate, carbonic acid, sodium chloride, mercuric chloride.
5. Write the formulas of all the salts that can be formed from CF. the following ions: Ca + +, Mg++, Fe+++, A1+++, SO 4 6. What are the properties of 2 and H+? How might each one be converted into the other?
,
7.
What
are the properties of the following substances: Cu,

,
Cu++ Ag, Ag+, C1 2 CF? 8. Describe some of the

tions of the following:
properties of the dilute aqueous solu-
HC1,
KNO
8,
H^SOi,
Na SO 4 KC1, CuCl*
2
,
CuS0 4
144
9.
Ch. VII!
How does
the evidence obtained from the heat of neutraliza-
tion support the ionic theory?

10. Write the principal reaction occurring when (a) NaCl dissolves in water; (b) a solution of sodium sulfate is evaporated; (c) concentrated HC1 solution is warmed.
equations represent all substances indicating that they are mainly ionized or un-ionized, as the case may be a solution of acetic acid is neutralized by one of sodium hydroxide; silver nitrate and potassium chloride solutions are mixed, giving a precipitate of silver chloride; dilute hydrochloric acid acts on a solution of sodium carbonate, giving CO 2 gas, water, and sodium chloride solution; zinc is put into a solution of
11. In writing the following
by formulas
copper
sulfate, giving a precipitate of metallic copper; concentrated sulfuric acid acts on solid sodium chloride, giving hydrogen chloride
gas and solid sodium sulfate; mercuric chloride solution is treated with hydrogen sulfide gas, giving a precipitate of mercuric sulfide,
etc.
12.
liter,
What
is
in
and (b) grams per 400 cc.?

13.
the concentration of OH~ in (a) equivalents per liter, when 0.37 g. of Ca(OH) 2 is dissolved
of acetic acid
is
A solution
methyl
violet as a certain solution of
found to give the same color with HC1. Which would neutralize
the larger proportion of base? Explain. 14. Define or explain the following terms: ion, electrolyte, degree of ionization, faraday, electron. 15. What is the degree of ionization of a weak monacid base if the concentration of the OH~ in a 0.5 normal solution is 0.002
normal ?
16.
(a)
What
acetic acid
2
3 2
if it is
C H O ~? (c) 17. How many

posit
1 g.
the concentration of H+ in a 2 molar solution of 0.006 ionized? (b) What is the concentration of Of the un-ionized acetic acid?
is
and
(2)
(c)
(a) faradays, (b) coulombs are required to deof each of the following ions at the appropriate electrode how long will it take using a current of 1 ampere: (1) +
Ni++,
(3) C1-, (4)
A1+++?
Arrange the following in order of their freezing points, starting with the highest: (a) 1 N-HC1; (b) 0.1 JV-HC1; (c) 1 AT-acetic acid; (d) 0.1 M-sugar; (e) 0.1 M-H 2 SO 4 (/) water.
18.
;
present in the final solution? (b) What is the quantity of each in moles? (c) What is the concentration of each in moles per liter?
2
19. 0.1-g.
atom
of
Zn
is
added to 0.05 moles of HC1
in
500
cc.
O.
(a)
What substances are
20. State
is
145
rent
what electron changes occur when (1) an electric curpassed through a copper wire; (2) metallic zinc dissolves in acid; (3) chlorine gas acts upon metallic sodium.
21. Outline experiments to or weaker than succinic acid.
show whether
glutaric acid
is
stronger
22. It has been found that solutions of
CuS04,
2
for any which is not, any which cannot be decided from the data. Magnetism can be assumed to be an ionic, hence additive property.
are magnetic, while solutions of LaCl 3 are not. From this information, mark whose solution you expect to be magnetic,
2
K MnO4
?
K SO4, Ba(NO and + any substance below

3) 2
Nd(N0 3 )
3,
and
and
for
KNO
CuCl 2
La 2 (Mn0 4) 3
La*(S0 4 ) 3
Nd 2 (S0 4 ) 3
CHAPTER
IX
COMBINING PROPORTIONS
Ionic Charges. The proportions in which ions combine to form neutral substances are readily derived from their charges. Conversely, when the formula of an ionizing sub1.
is known, together with that of one of its ions, the formula of the other ion is readily obtained. Examples have been given in Chapter VIII, paragraph 10. The ionic charges, as explained in Chapter V, depend on the number of electrons an atom gains or loses. The elements, H, Li, Na, K, have but one outer electron to lose, hence, on 1. The combining with other elements, take a charge of elements, Be, Mg, Ca, Sr, Ba, have two outer electrons and give the ions Be++, Mg++, etc. The atoms, F, Cl, Br, I, with seven outer electrons, add one to complete an octet, becoming
stance
F~, Cl", Br", I".
substance may be insoluble in water and fail to give in that way a direct indication of the number of electrons each atom has lost or gained; nevertheless, we may feel confidence in the conclusions from more
2.
Oxidation Number.
For example, FeO and Fe 2 O 3 are insoluble water but they dissolve in H+ as follows: FeO + 2 H+ = FerH- + H 2 O; Fe 2 O 3 + 6 H+ = 2 Fe+++ + 3 H 2 O. They can 2 OH~ also be formed from Fe++ and Fe+++ as follows: Fe++ = Fe(OH) 2 = FeO + H 2 O; 2 Fe+++ + 6 OH~ = 2 Fe(OH) 3 = Fe2 O 3 + 3 H 2 O. Now H+ is a substance which becomes H2 when it acquires electrons at a cathode and OH~ becomes O2 and H 2 O when it loses electrons at an anode; hence we conclude that the iron in FeO and Fe2 O 3 respectively, has the same number of electrons as in Fe++ and Fe+++. We shall call the charge which an element appears to have its oxidation
indirect evidence.
in
146
or state.
147
number
may
Zn
reason for using the word oxidation be illustrated by comparing the following reactions:
Zn"
1
The
1
2H + = Zn = Zn + \ O 2 = Zn + C1 2 = Zn + Cu++ =
""
Zn++
+ H2 + 2 e~
Solution of zinc in acid Solution at an electrode
ZnO
ZnCl 2 Zn++ + Cu
Oxidation by burning Chlorination
Displacement of
Cu by
Zn.
Each of these processes involves essentially the removal of the two electrons from each zinc atom. Although the third reaction
only is literally oxidation, the term is extended in a figurative sense to include them all. Accordingly, the oxidation number of zinc has been increased in each case from to +2.
3.
The
reverse process, a gain in electrons, or decrease in
oxidation number, is designated by an obviously general term, reduction. In the above reactions involving Zn, the H+, O2 C1 2 and Cu** have been reduced, the oxidation
, ,
numbers having changed as

oxygen,
to
2; chlorine,
to
1 to 0; follows: hydrogen, 2 to 0. 1; copper,
4. The oxidation number can be assigned with little ambiguity to elements that always lose the same number of electrons, such as H, Na, K, Mg, Ca, Al; however, there are
2 react to exceptions to ordinary behavior. Thus Li and melt from which form LiH, which fuses to give a conducting
2 separates at the anode, or pole from which electrons are being removed. The hydrogen apparently has the unusual 1, and the reaction is evidently charge, or oxidation number H" = J 2 0~~. Again, the oxygen in most of its compounds
H +
having gained 2 electrons per atom to complete the octet, as we might expect. It is otherwise, however, in a class of compounds called peroxides, including H 2 O2 BaO 2 Na2 O 2 Evidence for this is seen in
2,
, ,
has an oxidation number of
the following contrasting reactions:
BaO Ba0 2 SnO SnO 2
+ 2 H+ + 2 H+ + 2 H+ + 4 H+
= Ba++ + H 2 0, - Ba++ + H 2 O 2 = Sn++ + H 2 O, = Sn++++ + 2 H 2O.

,
148
It is
Ch. IX
evident that the oxidation numbers of Ba and O cannot be the same in both BaO and BaO 2 however, both give the ordinary Ba++ on reaction with acid, hence it is the oxidation number of the oxygen which changes. In the case of SnO and SnO 2 on the other hand, it is the tin that changes. 2 O 2 the oxidation number of Evidently in both BaO 2 and 2. If there were any the two atoms of oxygen together is evidence that the electrons were unequally distributed be;
,
tween the two oxygen atoms, one might assign different

2 oxidation numbers accordingly to the two atoms, for 2 just as do 1 and 0, for example, would add up to and 1, but not only is such evidence lacking but since
the two atoms are quite alike it is improbable that any such inequality could be more than instantaneous. The question has no practical significance it suffices to assign the oxidation
;
1 to oxygen in peroxides. number 5. Compounds whose atoms are held together by
electron-
pair bonds range gradually from those in which the electron pair is equally shared to those in which the pair is largely displaced towards one of the atoms. Such gradations are shown in Table 6, Chapter V. To assign the bonding electrons
entirely
to the more negative atom is evidently mther arbitrary except where the substance is ionic as with MgO, but it is customary in such cases to assign the electrons to
the more negative element. Usually, though not always, there is sufficient experimental evidence to reveal the direction of electron displacement, permitting useful classifications of the compounds of an element according to the several
oxidation numbers
for reactions in
it assumes, and the balancing of equations which the element changes its state of oxidation by simple formal procedures (cf. Chapter XV). 6. Thus, SF 6 SO 3 SO 4 ~~, and H 2 SO 4 are classed together as compounds containing sulfur with an oxidation number of + 6; with SC1 4 SO 2 and SO 3 it is +4; while in H 2 S, 2. These oxidation numbers are assigned and ZnS it is SH"~,
,
,
aid of the knowledge that oxygen has a very strong tendency to add 2 electrons in all its compounds except the
by
-COMBINING PROPORTIONS
149
1, hydrogen is usually 1> peroxides; chlorine is usually 2. Furthermore, the changes involving no change and zinc in oxidation number are simpler than those which do.
Compounds of oxidation number
arsenic are readily classified according to in the accompanying table.

TABLE
i
Oxidation Numbers of Arsenic
-3
HsAs MgsAsa
'As
+3
AsCl 3 As2 Os ~~
+5 AsF5
As2 Os
AsO2
7.
AsO3
~~
thiosulfate,
The
is presented by the sulfur in sodium the "hyposulfite of soda" of photography. thiosulfate ion probably has the structure,
An
interesting case
Na S 2O
2
3,
:O:S:S:
like that of
SO 4
This ion can decompose to give
off the extra

:,
sulfur as free sulfur,
whose atoms are
or as sulfide ion, :S
depending upon the reagents used. We might accordingly say that 4 and the inner and outer sulfur atoms are respectively either 6 and 2, depending upon which behavior we are consider0, or
ing, or, neglecting these behaviors, average for the two atoms. Decision
we might
Assign
2 as the
is
between these alternatives
quite unnecessary for balancing an equation for the oxidation of this ion, since a total of 8 electrons would be necessary to oxidize S 2O 3 to 2 SO 4~~.
"
another kind of combining value called coordination number of atoms, irrespective of charge, number, that group themselves around the atom in question. In sulfate ion
8.
is
There
that expresses the
and
is 4.
thiosulfate ion the coordination
number
of the central
atom
with a charge of 1, has a coordination number of 2 in the compounds, Ag(NH 3 ) 2+ and Ag(CN) 2~. Platinum, in PtCl 6 has a coordination number of 6, although it may be 4 oxidation level. regarded as containing Pt at the
In
it is 6.
SF 6
,
Silver,
150
PRINCIPL
.
CHEMISTRY
--E 2
Ch. IX
Examples of Coordination and Oxidation Numbers of the Central

Coordination
Atom
Oxidation
number
number
6 6
S04
~~
4
6 6 6 6
2 2
SFe K 2SiF6
4
3
2
1 1
Fe(CN) 6 Fe(CN) 6
Ag(NH 3 2+ Ag(CN)r K 3 P04 K S04 KC104

) 2
Cr(NH 3 ) 6 -CrO4
Table
2,
+++
4 4 4 6 4
6
7
which gives examples of coordination numbers and oxidation for a number of substances, should be of assistance in distinguishing them. The coordination number seems to be partly determined by geometrical considerations, depending on the relative sizes of the
numbers
central
ing structure, especially as
and surrounding atoms and upon the symmetry of the resultpacked into a crystal lattice. A larger
coordination
number
,
is
and smaller
of
size of the
favored by larger size of the central atom surrounding atoms, as shown by the existence
,
.
SF 6 but
9.
not SC1 6 OsF 8 but not FeF 8 K 6 IO 6 but only KC10 4 Covalenceo There is still another term in use, covalence,
signifies
which
(cf.
the
number
of electron-shared bonds con-
necting the element in question with surrounding elements
Chapter V, paragraph 10). This is particularly significant in organic chemistry, where relatively nonpolar, covalent bonds predominate. The element carbon gives no simple ions. Oxidation numbers, if desired, have to be based upon the
direction of displacement of the electrons in bonds, often small and uncertain. However, it is the covalence of carbon,
the
number of electron-pair bonds it can form, which is of far greater significance. This number never exceeds 4. (This matter is set forth in detail in Chapter XVI II.)
12
10.
it is
151
Writing Equations. In connection with chemical equaimportant to realize that the mere writing of the equation imposes no obligation upon the substance involved to behave as indicated by the equation. The burden is rather upon the one who writes the equation to endeavor to make it cortions
respond to an actual or possible behavior. A complete justification of an equation would require the experimental determination both of the substances produced, their formulas,
and
their relative
amounts.
A knowledge of oxidation numbers

"balance/* a necessary feature of
aids in writing the formulas of substances likely to be formed and also in fixing the numbers of atoms and molecules neces-
sary to
make an equation
an equation. 11. Union
of ions. Equations involving the mere splitting of molecules into ions or vice versa are easily balanced with
due regard to electric neutrality. For example, if a solution is mixed of A1 2 (SO 4 ) 3 which contains A1+++ and S0 4 4 and 2 with one of BaCl 2 which contains Ba* Cl", the SO 4 unites with the Ba++ to form a precipitate of BaSO 4 hence
, ,
"
we
write simply,
Ba++
+ S0 4
"~
= BaS0 4
The AI+++ and CP which
are present have not reacted, so that they need not be put into the equation any more than the water, the containing vessel, or other necessary feature of the reaction.
12. Let us consider, next, the reaction between aluminum and Fe3 O 4 to form aluminum oxide and iron. To be absolutely certain of the formula of the aluminum oxide produced we would have to determine it by analysis. We do not, however, find aluminum compounds in which the oxidation number of aluminum is other than 3, as we see it in A1C13 This would lead us to anticipate that the oxide formed would be A1 2 O3 which is correct. Accordingly, we have Al and Fe3 O 4 giving A1 2 O3 and Fe. We must next adjust the number of molecules so that there will be the same number
. ,
152
Ch. IX
atoms of each element on each side of the equation. It is obvious that we must take 3 Fe 3 O 4 to get an integral number, 4, of A1 2 3 molecules. Adjusting the number of atoms of Al and Fe, we have as the equation
of 3
It
is
Fe 3 O 4
8 Al
9 Fe
4 A1 2
always desirable to check the equation written by comparing the number of atoms of each element on each side of the equation. They should, of course, be equal. 13. Oxidation and Reduction of Simple Ions. Equations for simple reactions of this type are readily balanced by
balancing the total changes in oxidation numbers the increase for the substance oxidized must balance the decrease for the substance reduced. Examples of this process may be seen in the following equations
;
+ Cu. Zn++ + 2 Ag. 2 Ag+ C1 2 + 2 Br~ = Br2 + 2 Cl". Fe+++ + r = Fe-H- + \ 2 Fe+++ + Sn++ = Sn++++ + 2 Fe++.
Cu++
Zn-HI
.
+ Zn = + Zn =
(The balancing of more complicated equations involving oxidation and reduction is explained in detail in Chapter XV.)
Exercises
1. What is the probable oxidation number of each element each of the following compounds: CuSO4, Cu(NO 3 ) 2 Pb(NO 3 ) 2
,
, ,
in
PbCO 3
2.
CrCl 3
MgO,
NH
4 C1,
CuS,
FeCO 3
KC1O 3
CrO 4
Fe(OH) 2 ?
Write the formulas of a number of other compounds that be formed from the constituent parts of the above compounds might
(omitting the atoms within the ions). 3. Explain the terms: oxidation number, coordination number, oxidation, reduction, covalence.
4.
Complete and balance the following incomplete equations: Fe 2O 3 + C = CO +
Mg(OH) 2
+ 2 H+ =
MgO + 2 H+ =
153
+ KOH = Al + HgCl = Hg + A1+++ + CP NH + + Ca(OH) = NH OH +.

CrCl 3
2
5. Classify according to the state of arsenic the following arsenic compounds: AsCl 3 As 2O 3 As2O 5 As2S 6 NaAsS 2 (consider the oxidation number of S to be 3 As, 3 AsO 4 2), Ag 3As.
,
,
,
In each of the following reactions determine what elements are oxidized and what reduced
6.
:
HgCl 2
Sn++
= Hg 2 Cl 2 + Sn++++ +
2 2.
Zn
7.
~ + OH~ + H O = HZnO + H
2
Explain
Is
,
why both
positive
and negative oxidation numbers

(1)
are used.
8.
As
(2)
to
As 2O 5
oxidized or reduced 3 As to As 2 O 3 (3)
when it is changed from ? As 2O 5 to AsO 4
AsCl 3
9. Classify the following substances according to the state of oxidation of the sulfur in them: HS0 3~, SH~~, S, SO 4 2 S, SO 2
SO Na 2 S 2O 3 SC1 4
3,
,
ZnS.
10. Classify the following substances according to the state of oxidation of the iron in them: Fe2(SO 4 ) 3 FeS, Fe, FeSO 4> FeCU,
----
Fe(CN) 6
Fe 2
3,
Fe(OH) 2 KFe(SO 4 ) 2 -12

,
O,
BaFeO 4
CHAPTER
CHEMICAL NOMENCLATURE
1. The common names of most familiar substances, given before the development of chemistry as a science, usually give no clue to their composition. However, as the number
of
to use
known substances has increased it has become necessary names which are based upon some system. The multi"copperas"
(which is not an (which contains no copper), "Glauber's salt," "cream of tartar/ "muriatic acid," etc., would place an almost impossible task upon the memory if it were extended to the hundred thousand or more known substances. To avoid such a situation as is found in mineralogy, where the terms give little clue to the composition of the substance, chemists have evolved a nomenclature which is based upon the elements composing the compound. This nomenclature has the advantage of being almost international, so far as the European languages are concerned. 2. Names of the Elements. The only generalization possible in the nomenclature of the elements is in regard to the names of the metals. The effort has been to give the Latin neuter
oil),
1
plication of terms such as "oil of vitriol"
-um, to the names of metals, as illustrated by potassium, magnesium, platinum. Where the element was commonly known before the introduction of this systematic nomenclature we may have still surviving the common name without this suffix, as with iron, silver, copper, gold. In such cases the Latin name, from which the symbol is derived, may, however, often be used to designate compounds. For example,
suffix,
instead of copper sulfate we may say cupric sulfate, from the Latin cuprum. The reason for this use of the Latin name
vill
become apparent
later.
154
The group
155
which gives compounds analogous to those of the metal potassium, is called ammonium. 3. The More Positive Element Named First. It is cus,
NH 4
tomary to give the name of the metallic or positive element first in naming the compound (corresponding to the order
used in writing the formula), as
is
seen in the
aluminum
sulfate,
etc.
oxide,
sodium
chloride, copper sulfide,

fluoride,
names of magnesium
potassium nitrate, hydrogen
carbon dioxide,
Binary Compounds Designated by Suffix -ide. When the compound consists of but two elements it is customary to add the suffix -ide to the name of the second or less metallic element in naming the compound. Thus all compounds of oxygen with a single more positive element are called oxides,
4.
those of chlorine are called chlorides, those of phosphorus, phosphides, those of carbon, carbides, etc.
In a few cases this suffix

of certain groups acting
is
used where the compound
contains more than two elements because of the existence
example, the cyanide group,

;
much like a single element. For CN, acts very much like the
is called potassium cyanide, by analogy halogens hence with KCl, potassium chloride. 5. Designation of Compounds Where the Positive Element
KCN
Numbers. As was pointed there are many elements showing more out Chapter IX, than one oxidation state in their compounds, so that the
Different Oxidation
in
May Show
simple naming of the constituents as above leaves an ambiguity as to which of the possible compounds is meant.
There
are, for
cury, iron, tin, in these cases, to speak of mercury chloride, iron chloride, tin oxide, copper sulfide, etc. In most cases the positive elements exhibit but two oxidation states, and it is possible
example, two chlorides, oxides, etc., of merlead, copper, etc., so that it is not sufficient,
to distinguish their two series of compounds by adding the suffixes -ous and -ic to the name of the positive element,
signifying the lower
Accordingly,
we
designate
and higher oxidation states respectively. Hg2 Cl2 as mercurous chloride and
156
Ch.
HgCl 2 as mercuric chloride; As2 O 3 as arsenous oxide, and As2 O 5 as arsenic oxide. In many cases the common English
name of the element does not lend itself to this usage, as with the elements iron, copper, tin, lead. In such instances the Latin name of the element is used, so that we have FeCl 2 ferrous chloride, and FeCl 3 ferric chloride, Cu 2 O, cuprous oxide, and CuO, cupric oxide, SnS, stannous sulfide,
,
,
and SnS 2 stannic

,
sulfide.
Another way of distinguishing between different compounds of the same element is by the use of the Latin and Greek numeral prefixes to the names of the elements. These prefixes,
up
to eight, are as follows:
1234
BiTerTri-
678
SexaSepti-
Latin
Uni-
QuadriTetra-
Greek
Mono-
Di-
QuinquePenta-
OctaOcto-
Hexa-
Hepta-
To
these
we may add
sesqui-,
meaning one and a
the Latin hemi, meaning one half, and half. By the use of these prefixes
we can often designate the compound with less ambiguity than by means of the suffixes -ous and -ic, especially when more than two compounds exist. As examples of the use of these prefixes we may mention CO, carbon monoxide, and CO 2
,
carbon dioxide;
disulfide; PCla,
CS 2
called
both carbon bisulfide and carbon
phosphorus trichloride, and PCls, phosphorus Cr2 Oa, chromium sesquioxide, and CrOs, chromium trioxide; Sb2 Sa, (di)antimony trisulfide (antimonous sulfide) and Sb 2 Ss, (di)antimony pentasulfide (antimonic sulfide).
pentachloride
;
numerals are used to indicate the state of oxidation alone, without commitment as to the particular combination in which it exists, e.g., plutonium IV or Pu^.
6. Binary compounds containing oxygen in the same peculiar form as in hydrogen peroxide are called peroxides, e.g., BaO 2 barium peroxide, Na2 O 2 sodium peroxide. 7. Binary Acids. Acids consisting of hydrogen and one other element are designated by the prefix hydro- and the suffix -ic,
,
,
Roman
like
HC1, hydrochloric acid; HNa, hydrazoic acid;
2 S,
hydro-
sulfuric acid.
10
8.
157
Oxyacids and Salts. Certain elements capable of assummore than one oxidation state form two or more acids ing containing oxygen. In such cases the significance of -ous and -ic in distinguishing higher and lower oxidation state is similar to that used with binary compounds. We have H 2 SO3, sulfurous acid, and H 2 SO4, sulfuric acid; HCrO 2 chromous acid, and H 2 CrO4, chromic acid; HaAsOa, arsenous acid, and H 3AsO4, arsenic acid; and HN0 2 nitrous acid, and HNO3 nitric acid. When more than two oxygen acids of the same elements exist, the prefixes hypo- and per- are used, as illustrated in the following table, which shows at the same time
,
,
the salt designations corresponding to the different types of acid, using the acids of chlorine for illustration:
Acid
Corresponding Salt
HC1
Hydrochloric
KC1
HC1O
HC1O2
Hypochlorous Chlorous
Chloric
Perchloric
KCIO
KC1O2
HC1O 3
HC1O4
9.
KC1O 3
KC1O4
Potassium Potassium Potassium Potassium Potassium
chloride
hypochlorite
chlorite
chlorate
perchlorate
Peroxy-Acids and Salts.
few oxygen acids and
salts
contain a pair of oxygen atoms joined together as in hydrogen peroxide. These are designated by the prefix peroxy. An ex2 SO 5 peroxysulfuric acid, in which it is part of the not the sulfur- which has the unusual oxidation numoxygen, ber (cf. Chapter IX).
ample
is
There are many cases where though the corresponding acids are not capable of existing free. These are designated in the same way as the oxysalts, using the prefix sulf(o)~, or better, thio-. We have KSbO 2 potassium antimonite, and
10. Sulfoacids
and
Salts. in
sulfur
replaces oxygen
salts,
potassium thioantimonite KSbO 3 potassium antimonate and KSbSa, potassium thioantimonate KCNO, potassium cyanate, and KCNS, potassium thiocyanate. In the case of Na 2 S 2 Os, which seems to be a sulfate with one oxygen atom replaced by a sulfur atom, the name thio-
KSbS 2
sulfate
is
given.
158
Ch.
11. Complex Halogen Acids and Salts. Similar to the oxy- and sulfoacids we have others containing the halogens, like H2PtCl6, chloroplatinic acid, giving salts called chloro-
platinates;
2 SiFe,
fluosilicic acid
(cf.
H 2 SiO3
,
silicic
acid);
chloroaurous acid and HAuCl 4 chloroauric acid. 12. Acid and Basic Salts. Many acids have more than one replaceable hydrogen atom in the molecule, and many bases
HAuCl 2
have more than one replaceable hydroxyl group in the molecule. Sulfuric acid, from example, is called a dibasic acid on account of its ability to neutralize two hydroxyl groups.
Similarly,
H PO 4
3
phosphoric acid,
,
is
the other hand,
Mg(OH) 2 magnesium
hydroxide,
a tribasic acid. On is a diacid
6ase for similar reasons. In such cases it is usually possible to have partial neutralization of either acid or base so as to give either an acid salt or a basic salt. The following equations represent the formation of such salts
:
NaOH + H 2 SO 4 = NaHSO 4 + H2 O, KOH + H PO 4 = KH 2 PO 4 + H2 O, 2 KOH + H 3 PO 4 = K2 HPO 4 + 2 H 2 O,

3
Mg(OH) 2
The
salts
HC1 = Mg(OH)Cl
+ H 2 O.
produced in these reactions would be called, respectively, sodium acid (or hydrogen) sulfate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate and magnesium hydroxy chloride or basic magnesium chloride. The names monoprotic, diprotic, etc., are used by some
chemists in place of the preceding, signifying
1
proton (hydro-
gen ion), 2 protons, etc. Sometimes a basic or
hydroxy salt may lose water, becoming an oxysalt. With bismuth hydroxide, for example, Bi(OH) 3 the progressive neutralization with HC1 would
,
give
first
first
Bi(OH) 2 Cl, then Bi(OH)Cl 2
of these loses water,
finally BiCl 3 The BiOCl, a well-known becoming

,
substance called bismuth oxychloride. In naming these two kinds of basic salts chemists are not always careful to distinguish between an oxysalt and a hydroxy salt, but there
13
is
justification in this,
159
some
existing in
many
is
on account of the uncertainty cases as to whether the water present in
the precipitate
actually combined or not.
radical, existing throughout various metathetical reactions. The radical is then usually designated by the suffix -y/, as in
Sometimes
this
oxy group plays the part of a
BiOCl, bismuthyl chloride, CrO 2 Cl 2 chromyl chloride, UO 2 Cl 2 uranyl chloride. Acid salts may likewise lose water, but the possible types of compounds can best be understood in connection with
,
the various types of partially dehydrated acids. 13. Partially Dehydrated Acids and Their Salts.
If
an
it
potassium acid sulfate, loses water according to the equation

acid salt like
,
KHSO 4
2
is
heated,
KHSO 4 = H 2 O + K
S2 O 7
The same
result is obtained
by adding SO 3
is
to
K SO 4
2
With
reference to its
mode
of formation this salt
pyrosulfate (from the Greek pyr, meaning be called potassium bisulfate on account of the extra SO3 present. This is more evident if the formulas of both the
called potassium fire). It may also
and the bisulfate are expressed as compounds of acid and basic anhydrides, as was done in Chapter V for many 2 SO 3 respectively. There salts, giving K 2 O SO 3 and K 2 O other examples of this type. When acid is added to a are chromate, as K2 CrO 4 instead of getting an acid salt, KHCrO 4
sulfate
,
there results a bichromate, as represented
by the equation
CrO 4
HC1 = (KC1
+ KHCrO
4)
= KC1
+ H 2 + I K2 Cr2
7.
There is no great distinction between a bisalt and an acid salt (in solution it is generally impossible to distinguish them), so that the former name is applied somewhat indiscriminately. Thus called sodium bicarbonate,
NaHCO3
sodium acid carbonate, is often though the real bicarbonate, which

,
would be Na 2 C 2 O5, does not exist. Similarly KHSO 4 may be called potassium bisulfate. Sometimes it is possible to,
160
Ch.
have still more of the acid anhydride present, as with K2 Cr3 Oi and K2 Cr4 Oi 3 called potassium trichromate and tetrachromate, respectively, or in general, polychromate (from the Greek poly, meaning many). This again becomes most obvious when the formulas are written in terms of the acid and basic anhydrides, giving K2 O 3 CrO3 and K2 O 4 CrO3 It might be desirable to be more precise, reserving the name potassium acid sulfate for KHSO 4 and potassium bisulfate for K 2 S 2 O 7 but it is unlikely that the familiar name for NaHCO3 sodium bicarbonate, would give way in the interest of a finer distinc,
tion.
With a
exist
tribasic acid like phosphoric acid,
several
relations
partial
anhydrides,
like
is
HPO3
H PO 4 there and H 4 P Or.

3
,
The
between these acids

3
best brought out
by
the equations,
In
H 2 O + P2 O 5 = 2 H P0 H 2O + P O = 2 HPO3 = 2 H PO - 2 H O, 2 H O + P O 5 = H 4 P2 O = 2 H PO 4 - H O. the first, H 3 PO 4 we have the maximum amount of water,

3
4,
and
it is
called orthophosphoric acid (from the

straight, direct).
Greek
ortho,
second, metaphosphoric acid meaning the Greek meta, meaning. after), may be derived by (from the simple abstraction of water from the orthoacid. The third is called pyrophosphoric acid. The application of these terms
The
to several other acids, as in the following table, will
make
them
Acids
clearer:
Ortho
Meta
Pyro
and
is
is no distinction between a pyroacid and a polyacid, and where there are several it not customary to use the prefix pyro- with its ambiguous
It is
evident that there
its salts
13
number
161
significance, for although there is
but one pyrophosphoric
of polysilicic acids, which require such distinguishing terms as dimetasilicic acid for 5 2 Si 2 trimetasilicic acid for 2 Si 3 7 diorthosilicic acid for 4 Si 2 O6,
acid there are a
H H
etc.
The
salts are, of course, designated as for the simpler

is
acids;
phate,
thus Na2 H 2 P2 C>7 Na2 B 4 O7 (borax)

3 is
disodium-dihydrogen pyrophos-
is
sodium
tetra- (or pyro-) borate,
K Sn0
2
potassium metastannate.
Exercises
1. How should each of the following substances be named: CaH 2 H 2S, PbS, Ni(OH) 2 Ni(OH) H g2S0 4 HgSO 4 PbO, Pb 4 NH 4 C1, NH 4OH, CuC0 H 2 C0 Hg(N0 3 ) 2 Hg(OH)N0 NH 4HSO 4 KHNH 4 PO 4 SbCl SbCU, SbOCl, NaCl, NaCIO, NaH 2A10 NaAlO 2 S0 2 H 2SO 3 (cf. H&O*, A1C1 A1(OH) Na 2S 2 SO Sb 2 3 ? sulfuric acid), NaHSO
, ,
3,
3,
3,
3,
3,
3,
3,
3,
3,
3,
2.
Give the names of the following substances:

(3)
(1)
C1O 3~~;
(2)
NaCIO;
HBr;
(4)
HC10
(5)
KIO 4
about the following substances can be concluded from their names: thallium; silver arsenide; thallous chloride; carbon bisulfide; phosphorus pentabromide nitrogen iodide;
3.
What
facts
cerium; eerie chloride; lead dioxide? 4. Give the formulas of the following substances:
gas; (b) carbonate radical;
(c)
(a)
oxygen
hydroxide; (d) cuprous sulfide; (e) aluminum sesquioxide; (/) nitrogen trichloride. 5. If 3AsO 4 is called arsenic acid, what should each of the
ammonium
following be called:
6.
If
4
HAs0 H As0 3 H 4As 2

3, 3
,
7,
PbHAs0 KAsS
4,
3?
K MnO
2
is
called
potassium manganate, what should
KMnO
7.
be called?
If
SnO 4
is
called orthostannic acid,

3,
each of the following:
H^nO* NaHSnO NaHSnO Na

,
what would you call 2 2 SnS 3 ?
CHAPTER
XI
THE SPEED OF CHEMICAL REACTIONS

1. The Problem. The previous chapters have been taken up with various aspects of the nature and composition of substances, and with the representation of substances and their reactions by means of formulas and equations. We
are
now ready
to inquire into the
means
of controlling chemi-
or prevent undesirable ones. There are two factors involved in this control, the direction and the speed. For example, at high temperatures the following reaction takes place readily:
cal reactions so as to realize desirable possibilities
NH = N + 3 H
3
2
2.
shows that it to be developed in Chapter should be possible to reverse this reaction at low temperatures and make ammonia from its elements. We find by experiment, however, that the reaction proceeds so slowly at low temperatures as to be utterly useless as a means of making ammonia, and that we must seek some means for its acceleration in order to make it of any practical use. The means of altering the direction of a reaction will be discussed in the following chapters, this one being devoted to the question of speed in reactions where the direction is already assured. Sometimes we may wish to increase the speed of a reaction, as in the cooking of food, and sometimes we may wish to retard an undesirable reaction, such as the rusting of iron or the decay of wood. How may this be done? 2. Application of the Kinetic Theory. In order that reaction may take place between different substances, their molecules
The theory
XV
must come together, or collide. However, when we calculate from kinetic theory the number of collisions, and compare our
162
SPEED OF CHEMICAL REACTIONS

number
discover that
163
calculation with the observed
of molecules reacting,
we
by no means every
collision leads to reaction.
In a typical reaction, only one-millionth or less of the collisions lead to reaction; most colliding molecules merely bounce off. To increase the speed of a chemical process, we can either
number of collisions, or increase their effectiveness by making them more violent. The first is achieved by a greater concentration, the second by a higher temperature.
increase the
3. Effect of
number
of collisions
Concentration. Kinetic theory tells us that the is proportional to the concentration of
molecules. In agreement with expectation, we do find all reactions to be faster at higher concentrations of their reactants.
For example, combustion is much more rapid in pure oxygen than in air, which is only one-fifth oxygen carbon dioxide gas is evolved rapidly when sodium bicarbonate is treated with dilute hydrochloric acid, but at a much more moderate speed with the weak acid, sodium dihydrogen phosphate. Chemists constantly make use of this effect of concentration
;
to control the speed of reactions. Thus, high pressures of nitrogen and hydrogen will increase the speed of the ammonia
reaction which at ordinary concentrations is too synthesis. fast to study (such as, for example, the reaction of iodine with
thiosulfate ion in solution) can be slowed extremely dilute solutions.
4.
If
down by
the use of
two molecules have to

;
collide in order to bring
about a
certain reaction, then doubling the concentration of either should double the speed of the reaction doubling the concentration of both should quadruple the speed. Of course, as the reacting substances
are used
up the speed diminishes.
quantitative relation between reaction velocity and concentration is expressed by an equation of the general type,
V
The
the velocity of reaction, as measured by the rate of disappearance of one of the substances, or of the formation of another; and Ci, c%, c 3 etc., denote the concentrations of one or more kinds of
where
is
reacting molecules. This sort of expression
is
called a rate law.
164
the reaction of iodate with iodide,
5 I-
Ch. XI
As an example, take
IO 3
-
+ 6 H+ =
is
3 I2
+ 3 H O.
2 2
.
The
rate law for this reaction

v
found to be
2
(iOr)(i-) (H+)
As may be seen from this example, the exponents in the rate law do not necessarily correspond to the coefficients of the balanced equation for the reaction. For this reason, the rate law for a reaction cannot be inferred from the balanced equation, but has to be determined
experimentally.
5.
Surface Reactions.
speed
is
face, its
a reaction is taking place at a surproportional to the surface area. For this

If
reason, finely
powdered sugar
will dissolve faster
than lump
sugar; a spray of droplets will evaporate faster than a still body of liquid; and a combustible dust will burn in air with
explosive rapidity. For the same reason, solids used as catalysts are usually prepared in a colloidal state of subdivision, or are
deposited on other solids of very great surface area. * The condensation of vapor on a droplet, or the growth of a
crystal from a liquid, likewise proceeds at a rate proportional to the surface area. At the beginning of the process, when the
area
to
is
zero, the rate is also zero. Consequently,
it is
necessary
start the condensation or crystallization. In the complete absence of nuclei, it is quite easy to cool a vapor well below its condensation temperature, a
liquid
add "seeds" or "nuclei" to
below
its
freezing point, or a salt solution below its
saturation
finds that
temperature,
thus
forming
organic
"supersaturated"
systems.
An
"supercooled" and chemist frequently
a compound he has prepared will not crystallize until a "seed crystal" of the same substance has been added. Another application of nucleation is the cloud chamber, in which the path of an ionizing particle appears as a fog track formed by the condensation of droplets upon the ions, which act as nuclei. Another is the initiation of rainfall by the nucleation of clouds.
The photographic
process
makes use
of
it
nucleation:
when
light strikes
a grain of silver bromide,
165
produces a tiny nucleus of metallic silver, at whose surface chemical development later takes place preferentially.
6. Effect of
Temperature.
We
find that the effect of increas-
ing the temperature is always to increase the reaction velocity. An increase of 10 C. in temperature will generally double or
triple the speed of the reaction. This is merely a rule of thumb; the temperature coefficient varies a good deal from reaction to reaction. For example, the rate at which sugar dissolves in
may increase some 25% upon a 10 rise in temperature, while the rate of a protein reaction, such as the coagulation of egg white, may increase 30-fold upon the same temperature rise.
water
Chemists make use of the accelerating effect of higher temperature in chemical reactions, and we see it constantly in everyday life. The reactions responsible for the growth of plants, for the decay of dead animal and plant substances, for the souring of milk, are all greatly influenced by the tem7.
perature, so that the importance of warmth for growth and of cold storage for preservation is well known to all. The housewife sets her bread to rise in a warm place to hasten the
fermentation which produces the carbon dioxide. Those who have lived or camped at high altitudes know of the difficulty of cooking certain foods at the lower temperature at which water boils under such conditions. The difficulty is sometimes
which hold the steam under pressure, allowing a higher temperature to be reached. Such an apparatus may also be used at ordinary altitudes, resulting in a great saving of fuel when cooking such things as beans or the tougher cuts of meat, for it requires scarcely any more fuel to maintain a temperature of 120 C. than it does to maintain one of 100 C., although a reaction that requires 5 hours at the latter temperature might be completed in less than 1 hour at the former. In such processes as extracting glue, gelatin, and fats, "superheated steam" is used with similar effect. The speed of cooking such a thing as a potato is also,
solved
of "pressure cookers,
by means
"
increased by cutting it into small pieces, so that all parts of it are quickly brought to the temperature of the boiling water
in
which
it is
immersed.
166
Ch. XI
8. The process of hardening steel is an interesting case of retarding a reaction by lowering the temperature. Above 766 C. a steel containing 0.9 per cent carbon consists of a
hard, tough variety of iron holding the carbon in solid solution, but below that temperature it tends to change into a
heterogeneous mixture, shown in Fig. 3, Chapter I, of soft iron (like wrought iron) and a hard, brittle iron carbide,
FeaC, known as cementite. However, this transition requires an appreciable time, and if the steel, heated above 725 C., is suddenly cooled by quenching in water, so that low temperatures are quickly reached, the tough solid solution may be obtained at ordinary temperatures, where the velocity of the change is practically negligible. This is shown in Fig. 4, page 9. A solution which required 10 seconds for transition
766 C. to the variety stable at ordinary temperatures would require 300,000 billion years at 20 C. if the reaction velocity were halved for every 10 C. fall in temperature.
at
is thus an unstable substance at ordinary but we can keep it almost indefinitely by reason temperatures of the extreme slowness of its change into the stable variety. If we cool the steel slowly, i.e., anneal it, or if we allow the hardened steel to get too warm for a while, as by too rapid grinding or cutting with a tool, it changes into the stable
Hardened
steel
soft mixture, losing its

9.
Many
chemical
"temper." substances
are
similarly
unstable
at
which they decompose is small. In ozone, Oa; hydrogen peroxide, H2O2J

of the
ordinary temperatures, existing only because the speed at this class are included
compounds
all explosives; and most of carbon. Nitric oxide, NO, is stable in
the true sense only at the temperature of a very hot electric arc and it can be obtained at ordinary temperatures by a process of rapid cooling similar in principle to the hardening of
steel.
10.
is
Combustion and Detonation. Spontaneous combustion
the result of the preliminary slow oxidation which many combustible substances undergo in contact with air. Ordinarily
the heat of these reactions
is
liberated so slowly that
it
has time
11
167
to be conducted away, so that no perceptible rise in temperature of the oxidizing material takes place. When, however,
the material
waste, and
is
a poor conductor of heat,
like oil-soaked
cotton
in large quantities, so that the heat produced is partly retained, then the rise in temperature causes an increase in the rate of oxidation, with a further gradual rise in temis
perature, until the temperature of ordinary rapid combustion is attained, and the material bursts into flames.
The temperature in a combustion zone is so high that most chemical reactions there are very fast. The rate of propagation of combustion is limited by the rate at which heat can be transferred, or by the rate of diffusion of hot molecules.
is a very rapid decomposition, in which the and pressure are extremely high, and which temperature
detonation
the velocity of sound. high explosive, such as nitroglycerine, detonates; so does a hydrogen-oxygen mixture, or the fuel in a "knocking" engine.
spreads through
its
medium with
The decomposition
fuel in
of gunpowder, of rocket propellants, or of
a properly operating internal combustion engine, is not detonation, but only a fairly rapid reaction. 11. Activation. The fact that only a small proportion of
collisions lead to reaction
can be related to the
stability of the
reacting molecules, indicating that they must first be "opened up" in some way before their atoms can rearrange themselves
molecules. Suppose, for example, that hydrogen or nitrogen can react only if they first split into atoms: the dissociation into atoms requires, for hydrogen, 103 kcal. per mole,
into
new
" "activation energy. may use a mechanical analogy to assist in understanding activation. Let us imagine a weight resting on a shelf provided
and for nitrogen, 226 kcal. per mole. For most reactions, it is not necessary to split molecules into atoms in order for them to react. However, virtually all reactions do require some
We
with a rim, as
in Fig.
1.
It will
be possible to
let
the weight
do work while falling to the floor by attaching it by means of cord and pulley to a dynamo or other means of absorbing energy. If the rim were absent and the weight standing on
168
shelf,
Ch. XI
a smooth, oiled
very
little
energy would have to be
expended
to push the weight over the edge
and
start the
process, but in the arrangement shown, it is necessary to do work on the weight to lift it over the rim in order to start the process. This extra energy is then re-
covered by reason of the extra height through which the weight

Energy of
activation
call the energy rethe weight over the shelf, from a to 6, the energy of activation, while the energy obtained from a to the floor, c, is the
falls.
We
might
lift
quired to
Energy of
reaction
net energy of the reaction. These
two amounts
of energy evidently
have no necessary connection.

12.
The necessary
activation en-
J
Fig. 1.
ergy must be derived from molecular
Illustration
of
differ-
ence between energy of activation and energy of reaction.
This is possible because the molecules of a gas have velocities

collisions.
The
both lower and higher than the mean velocity discussed in Chapter III. velocities are distributed among the molecules according to
curves shown in Fig. 2. At room temperature, are between molecules with a total energy of 1365 calories or greater; 1%, 2730 calories or greater; 1 in 1000, 4095 calories or greater, and
so on.
10%
of the collisions
One
collision in 10 9 involves
an energy of 12.3 kcal. or greater, and one collision in 1015 20.5 kcal.
or greater.
The number of high-energy

lisions
colVelocity
depends markedly on temperature. A 10 increase in temperature will double the number

of collisions of 12,3 kcal. or creater
Distribution of molecular Fig. 2. velocities at lower temperature, h
and hieher temperature.
T2
13

number
169
energy, and will triple the
of collisions with energy exceed-
ing 20.5 kcal. Consequently, if a certain reaction requires an activation energy of 12.3 kcal., a ten-degree temperature increase will
double
rate; for an activation energy of 20.5 kcal., the temperature increase will triple the reaction rate.
its
same
The
quantitative relation of the reaction rate constant,

is
k,
to
temperature
4.57 logio k
= A -
|,
where
E are quantities characteristic of the reaction in question; E is the activation energy for the reaction, in calories per mole. A graph of the logarithm of k against the
A
and
will give a straight line. reciprocal of 13. Effect of Catalysts. Many reactions can be accelerated by the presence of substances which are not themselves perma-
nently used
catalysts.
pathway
detailed
of a catalyst is to provide an additional or mechanism for the reaction; in many cases, the
up by The role
the reaction. Such substances are called
of the catalyzed reaction is known. As one example, we can take the old "lead chamber" process for the manufacture of sulfuric acid. In the absence of a
mechanism
2 is very slow; but in the catalyst, the reaction of SC>2 with of oxides of nitrogen, the reaction proceeds readily, presence
by the
following steps:
SO 2
+ 2 H O + 2 ONOSO H = 3 H SO 4 + 2 NO, NO + | = N0 NO + NO + 2 H SO = 2 ONOSO H.

2
2 4
2,
Here the reagent which actually oxidizes the SO 2 is nitrosyl bisulfate, ONOSO 3 H. Part of the NO produced by the reaction is allowed to react with O 2 and the resulting mixture of NO and NO 2 is used to prepare the nitrosyl bisulfate once more.
,
An
example of catalysis
-
in solution is
provided by the
re-
action of iodate with
sulfite,
IO 3
+ 3H
SO 3 =
I-
+ 3 SO ~ +
4
6 H+.
170
Ch. XI
This reaction can take place without a catalyst, but it can also be catalyzed by iodide ion, the steps of the catalyzed reaction being:
IO 3
I2
+ 5 I- + 6 H+ = + H SO + H O =
2 3
2
I2
2 I-
+ 3 H O, + SO* + 4 H+
2
In the catalyzed reaction,
duced by the
Since this
is
I 2 is an intermediate, which is proand rapidly consumed by the second. step reaction is catalyzed by one of its own products, it
first
called "autocatalytic."
A
gen
great
ion.
many
One
of these
reactions in solution are catalyzed by hydrois the conversion of the 12-carbon sugar,
sucrose, into equal
amounts
cose and fructose.
The
two 6-carbon sugars, glucalled "inversion of sugar/ reaction,

of the
first
bears the distinction of being the was systematically studied (1850).
small
reaction whose speed amount of acid is
sometimes added to sugar in making candy, since the resulting mixture of sugars does not so readily crystallize. It is interesting to note that honey is invert sugar. Naturally, a reaction which is catalyzed becomes slower if
the catalyst is removed or destroyed, and some reactions can be "inhibited" in this fashion.
14.
Contact Catalysis.
The "heterogeneous"
or "contact"
catalysts are solids upon adsorbed and there react.
whose surfaces molecules become
They are extensively used, both in the laboratory and in industrial processes. familiar laborais the addition of manganese dioxide, MnO2, tory example
is heated to prepare oxygen. Platinum will initiate the combination of hydrogen with oxygen on its surface. Some gas lighters and cigarette lighters have been constructed on this principle. Platinum is also used as the catalyst in the oxidation of ammonia to NO, and platinum (or vanadium pentoxide) is the catalyst in the "contact" process for the synthesis of SOs. In the union of nitrogen with hydrogen to give ammonia (the Haber process)
to potassium chlorate which
an
iron catalyst
is
used.
15
SPEED OF CHEMICAL Rf ACTIONS
171
The detailed mechanism of contact catalytic reactions is not known in most cases. There is evidence that the adsorption of hydrogen, oxygen, or nitrogen yields some dissociated atoms of these elements on the surfaces of metals like platinum or iron.
15.
Enzymes.
enzymes,
important class of catalysts, known as are produced by living organisms and catalyze
An
many
reactions.
The
ptyalin of saliva, whose function
is.
to
convert starch into sugar, the diastase of malt, which has a similar action, and the zymase of the yeast plant, which converts certain sugars into alcohol and carbon dioxide, are examples of important enzymes. Similar bodies are thought
to play fundamental roles in the processes of growth and nutrition of plants and animals.
are proteins, and accordingly are destroyed by high temperatures, as well as by many chemical reagents. number of enzymes have been isolated in pure, crystalline
Enzymes
form.
Exercises
1.
Define catalyst.
2.
Divide the catalysts mentioned
in the text into surface cata-
lysts
3.
and dissolved
catalysts.
What
effect
may
the use of a double boiler have on the speed
of cooking food?
4. What means could you employ for rapidly washing photographic prints free from the "hypo" of the fixing bath? 5. How might you alter the time required for developing a
photographic negative? 6. How might you endeavor to increase the speed of the reaction
BrO-r
6 I-
+ 6 H+ = 3 H O +
2
Br-
I2?
What
effect would acetic acid have upon the speed as compared with hydrochloric acid of the same concentration? 7. The organism existing in "mother of vinegar" converts alco-
hol into acetic acid
by the reaction
C 2 H BOH
By what means
= C2H O 2
4
H-
H O.
2
could the manufacture of vinegar be hastened?
CHAPTER
XII
CHEMICAL EQUILIBRIUM. THE EFFECT OF CONCENTRATION

1. Reversibility of Chemical Reactions. The problem of the control of chemical reactions involves not only the speed, as discussed in Chapter XI, but also the fact that most re-
have, therefore, two problems as distinct from each other as are the speed and destination of a train. To reach a desired destination quickly it is not
actions are reversible.
sufficient to get
We
on a
fast train; the train
must
also go in
the right direction. With chemical reactions, similarly, the conditions accelerating the reaction often reverse the direction at the same time. For example, the velocity of formation of SO 3 from SO 2 and O 2 increases with the temperature, but
the velocity of decomposition of SO 3 back into SO 2 and O 2 likewise increased thereby, and more rapidly than the velocity of its formation, so that SO 3 becomes increasingly
is
unstable at higher temperatures. Therefore, assuming that the time necessary for them to take place is allowed, we *vill turn our attention to the problem of the direction of
all
chemical reactions. Finally, in Chapter XIV, we will consider both effects together. 2. Most reactions are reversible, that is, the products of a reaction may usually be made to react with each other by suitable choice of conditions to produce the original substances. Many examples of this may be given. A liquid may be made to evaporate by raising the temperature or by reducing the pressure, and its vapor, conversely, may be recondensed to liquid by lowering the temperature or increasing the pressure. Solids may be liquefied by increasing the temperature, and liquids may be solidified by lowering the
172
CHEMICAL EQUILIBRIUM
173
temperature. Gases may either be dissolved in liquids or driven out of solution by suitable changes in pressure or
temperature.
The
naturally
CaSO 4
H 2 O, may
occurring mineral, gypsum, be deprived of part of its water by
moderate heating, giving plaster of Paris, which is approximately CaSO 4 \ H 2 O. When this is mixed with water the original dihydrate is re-formed, which causes the plaster to "set," due to the interlocking of the growing crystals of
2 2 O. Nitric oxide, NO, is decomposed by gentle into nitrogen and oxygen, and yet, at the high temheating perature of the electric arc a considerable amount of nitric
CaSO 4
be formed from the nitrogen and oxygen of air. Oxygen, O 2 is changed into ozone, O 3 by the silent electric discharge, and then gradually reverts to oxygen. When a lead storage battery is discharged, the lead dioxide of the positive plate, the lead of the negative plate and the sulfuric
oxide
may
acid in the solution react as follows:
PbO 2
Pb
+ 4 H+ +
is
SO 4
"=
PbSO 4
+ 2 H2 O,
and when the battery
recharged the reverse reaction takes
place, corresponding to the equation as read from right to left. When water charged with carbon dioxide passes over
limestone rock, the following reaction occurs:
CaC0 3 + H 2
The calcium
+ CO =
2
Ca++
+ 2 HCO ~.
3
ion dissolved in the water produces what is " called "hard water, and interferes with the cleansing power of soap by precipitating insoluble calcium soap. When this
water is boiled, however, the CO 2 is driven off, and the calcium carbonate is reprecipitated, corresponding to the equation as read from right to left. When steam is passed through a tube containing iron filings or nails heated to dull redness, the following reaction occurs:
3 Fe
+4HO =
2
Fe 3 O 4
+4H
2.
When
an excess of hydrogen is passed over the iron oxide, FeaO 4f under similar conditions, some of it is changed to steam
174
Ch. XII
with the reduction of the oxide to iron, exactly the reverse of the above. Illustrations of reversibility might be multiplied
ad
in
libitum.
3.
proof of reversibility consists simply each set of substances, as indicated by the two mixing sides of the equation, and seeking conditions under which the other set will be formed. The disappearance of any of the substances taken, or the appearance of any of the products, is usually sufficient proof that a reaction has taken place. Which particular substance to test for is determined by the
ease and decisiveness of the available tests.
tion of mercury, represented
2
The experimental
Thus the
oxida-
by the equation
2
Hg
HgO,
could be proved if conditions could be found under which mercury in contact with oxygen would increase in weight.
change in appearance corresponding to the red color of the oxide, or a decrease in the amount of the gaseous oxygen would suffice equally well. The reverse reaction, the dissocia-
mercury and oxygen, could be the red mercuric oxide and discovering proved by taking conditions of pressure and temperature under which there could be detected either the appearance of mercury or
tion of mercuric oxide into
oxygen, or else a loss in weight.

It is frequently desirable to express in the equation a reaction the fact that the reaction is reversible. This is done by substituting a double arrow, ^, for the equality sign. Written in this way, an equation such as the one above
4.
for
would appear as
follows:
2
It
Hg
2 *=*
HgO.
the
sign retains of the usual equality sign, merely adding further information, so that we would do well to regard it
full significance
must be remembered that the double arrow
as an abbreviation for a fuller representation such as the

following:
Since nearly
all
175
reactions are reversible, however, the double

superfluous. Its absence
arrow sign
is
somewhat
must never be
construed as indicating irreversibility. The double arrow can well be used where it is desired to emphasize that a reaction
has been observed to be reversible. A reaction which proceeds practically to completion

called
irreversible
is
often
and
is
2 CO 2 for arrow, as illustrated by the fermentation of one of the sugars, but the obligation to write a balanced equation often disappears when only a
frequently indicated CeHÔe * 2 C 2 5
H OH +
by a single
used instead of the more explicit =" 5. It is Possible to Have All of the Substances Involved in Reversible Reactions Present Together in Chemical
single
arrow
is
Equilibrium with Each Other. Instead of passing steam over heated iron in a tube, as in the experiment described above, we might simply heat them together in a closed vessel. We would expect, as before, the formation of some hydrogen and iron oxide, corresponding to the equation as read from
left to right. Likewise, if we heat hydrogen and iron oxide together at the same temperature and in a similar vessel, we would expect the formation of iron and steam, corre-
sponding to the equation as read from right to left. If we allow sufficient time for reaction in both cases, how will the final state of affairs in one vessel compare with that in the other? It is obviously absurd to expect either reaction to go to completion, just as it would be absurd to expect a ball placed on a certain table to roll all the way from a to b when we have previously found that, when placed at i, it rolls towards a. Obviously there must be some intermediate position on the table at which it tends to come to rest no matter at which end it is started. Again, if it is found that one body becomes cooler when brought into a certain room, and another becomes warmer when brought into the same room, it is evident that each body will come eventually to the same temperature, that of the room, which must lie somewhere between the initial temperatures of the two
bodies.
176
6.
Ch. XII
By
the same kind of reasoning,

if
it
should
2 O,
make no
or with heat them to a temperature at which they are able to react, in identical vessels, we will eventually get a mixture of all four substances in chemical equilibrium.
difference
whether we start with 3 Fe
+4H
Fe3 O 4
+ 4 HS,
we
The term signifies that the concentrations of the substances involved in the opposing reactions have become so adjusted or balanced as to equalize their rates, making the rate at which each substance is produced equal to the rate at which it is used up, so that there is no further net change in the
quantity. It is important to bear in mind that the constancy of these net quantities present does not mean that nothing is happening. The fact that the pressure of water vapor in
a closed vessel containing some pure liquid is constant at any fixed temperature does not mean that the same molecules remain always in the vapor phase; individual molecules are continually escaping from the liquid and an equal number being recaptured by the liquid in the same time. When we start with iron and steam, at a sufficiently high temperature, they react with a velocity depending on the concentration of steam molecules and on the surface of the iron. As these are used up the reaction gradually becomes slower. At the
same
time, as more hydrogen and iron oxide are produced, they begin to react with each other to regenerate the iron and steam, with an increasing velocity, until the rate of
of equilibrium
one reaction just equals that of the other. This conception was used in connection with simpler phenomena in Chapter III, and has an important bearing on what is
here to follow.
7.
Changing the Concentration of the Reacting Substances. When chemical equilibrium has been attained, it is possible to disturb it by any means which changes the relative speeds of the two opposing reactions. These rates may be affected by changing the temperature, or the total pressure on the reacting system, or the concentration of the substances involved. The effect of changing the temperature or total pressure will be dis-
The
Effect
on Chemical Equilibrium
of
XIV, and we
will turn
177
first
cussed in Chapter
our attention
to changes in concentration. 8. If we increase the concentration of one of the reacting substances, there are then more molecules of that substance
present in a given space, so that their ability to find and react with other molecules is increased. This will cause a
in the rate of the reaction using up this kind of molecule, until more of the products of this reaction, repre-
temporary gain
sented on the other side of the equation, are produced, so as to equalize again the rates of the two reactions. The net result is that the reaction proceeds to some extent in the
direction which will use
is
up the substance whose concentration
thus increased.
9.
,
For
,
SO3 SO2 and O 2

alyst.
illustration let us consider a closed vessel containing in chemical equilibrium, to attain which
requires a sufficiently high temperature
When equilibrium is the two reactions, represented

2
and perhaps a catattained we must imagine that
by the equation
2
SO 2
+ O2 =
SO 3
read in both directions, are taking place with equal velocities, with a net result of no change in the relative amounts of
the three gases present. Suppose, now, that more oxygen is introduced into the vessel. The increased number of oxygen
molecules will render
it
easier for
them
to collide with sulfur
dioxide molecules, resulting in a more rapid formation of sulfur trioxide molecules. As the number of the latter increase
own speed of decomposition will increase until the two reactions again take place at equal rates. The net effect of this increase in the amount of oxygen is to cause more of it to be used up, with a decrease in the amount of sulfur dioxide and an increase in the amount of sulfur trioxide.
their
The
adding or removing any of the three substances can be predicted on the above basis. present From a technical point of view, in making sulfur trioxide,
effect of
the important thing
is
to use
up the
sulfur dioxide as
pletely as possible, since the latter costs
commoney, whereas
178
Ch.
XM
the supply of oxygen is free. To accomplish this the kinetic theory indicates that it is desirable to have the oxygen in excess, since otherwise considerable sulfur dioxide would remain uncombined when equilibrium has been reached. 10. In general, after equilibrium has been reached, the
any change in the concentration of the reacting substances is to cause that reaction to take place which
effect of
tends to neutralize the change; that is, if the concentration any substance is increased, that reaction tends to take place which uses up that substance, and where the concentration of any substance is decreased, that reaction tends to take place which will replace that substance. This conclusion is a special case of a more general one, called the Theorem of Le Chatelier, which states that when equilibrium has been reached a change in any of the factors affecting equilibrium tends to make that reaction take place which will neutralize the effect of the change. (The discussion of other factors will be taken up in Chapter XIV.) 11. The above conclusion, in so far as concentration alone is concerned, is called the "Law of Mass Action/' or the "Mass Law." This name is slightly misleading, since it is not the masses of the substances present, but their concentrations, or masses per unit volume, which determine equilibrium. This point was discussed in Chapter III, where it was shown that the depth of the water in equilibrium with
of
vapor, or the extent of the surface between the two phases, has no effect upon the equilibrium. On the other hand, a
its
change in the concentration of the vapor, as by changing its volume, or in the concentration of the liquid, as by adding some other substance to it, 'would cause some reaction to
take
between
the equilibrium discussed above, steam, and hydrogen, the relative amounts of the solids have no more effect than would the addition of more salt to a saturated salt solution. The reacplace.
Likewise,
in
iron, its oxide,
tions occur at the place

solids
where the three phases, the two and the gas phase, are in contact, and these are not unbalanced by the excess of either solid.
13
CHEMKAi. EQUILIBRIUM
17V
Equilibrium in Solution. These same conclusions apply to reactions occurring in solution, including those between ionized substances. For example, that the reaction
12.
HC 2 H
will
= H+
+ C H (V
2
3
take place as read from left to right may be shown by taking pure acetic acid (which is un-ionized, as shown by its being a nonconductor) and dissolving it in water, when the solution will have the properties of hydrogen ion. That the reaction will also take place as read from right to left,
be shown by mixing a solution of a strong acid, like hydrochloric acid, giving a large concentration of hydrogen ion, with one of sodium acetate, which gives a large con-
may
We find that hydrogen ion disfrom the solution, and also that acetic acid appears partly appears, as is evident by its odor. It makes no difference, therefore, whether we start with a mole of acetic acid in a liter of water, or with a mole each of hydrogen and acetate ions in a liter of water, the final state of affairs is the same, which is that we will have present about 0.004 mole of each of the two ions and 0.996 mole of the undissociated molecules. If, subsequently, we add another mole of acetate ion (in solution with, say, sodium ion, which affects none of the substances present) some of the acetate ion will be able to
centration of acetate ion.
use up more of the hydrogen ion, becoming acetic acid, resulting in a considerable decrease in the acidity (hydrogen
ion concentration) of the solution. 13. The dilution of a solution of a
weak
electrolyte such
as acetic acid results in an increase in the degree of dissociation (cf. page 140), as can readily be deduced by the aid of
just as
the kinetic picture of equilibrium. At equilibrium there are many molecules of acetic acid splitting into ions as are being reformed from the ions in a given time. If more
water
is
added the rate of the ionization process can be
little
affected, since the acetic acid molecules in both solutions are
and
surrounded entirely by water molecules. However, the ""
H+
C2 HaO2
are farther apart, on the average, after the
180
dilution,
and cannot
collide
Ch. XII
and reunite so frequently, so that the former reaction gains upon the latter, and the resulting increase in the number of ions increases the frequency of till the rate of recombination again equals the rate
collision
of dissociation.
The
net result of the dilution
is,
therefore,
:
that more
of the acid has ionized as expressed
by the equation
HC2H O2 = H+ + C H 3O -.
3 2 2
14.
These conclusions are so important, and of such general
validity, applying to gaseous as well as ionic equilibria, that
emphasize them by the tabulation of the acetic acid equilibrium given in Table 1. The figures have been calculated by a method to be outlined later. Their relative, rather than
will
we
their
absolute,
magnitudes should here receive attention.
and B shows that the amounts of comparison of cases each of the three substances present at equilibrium are identical, regardless of the direction from which it has been
shows the large diminution of H+, and the HC2 H3 2 following an increase in H Case D shows the corresponding diminution of C 2 H 3 O2 ~", following the addition of an excess of H+. Case E shows the increase in the degree of dissociation caused by dilution. Chemists are accustomed to refer to the change from one condition of equilibrium to another, such as cases C, D, and E, as a shift of equilibrium to the left (Cases C and D) or to the right (E) as the case may be.
reached. Case
consequent increase in the amount of C 2 3 O2~~.
be noted that the equation, read either to the or the left, does not in itself tell how much material right has reacted or what are the equilibrium concentrations, but only that if acetic acid is allowed to ionize, due to putting
It is to
it into water, or by increasing the ionization by adding more water to a mixture in equilibrium, every molecule of acetic acid that ionizes forms one hydrogen ion and one acetate
if acetic acid molecules are formed, as by evaporaor the processes stated in B, C, and D, the ions unite tion, in the proportion one to one. In case C a large excess of
ion; again,
C2H 3O<f
had to be added to use up 0.0038 mole of H+, but
15
C2 H3 O2
"
181
out of the 0.1 mole added combined with H+. The presence of five hunters instead of one hunting for a rabbit in a certain tract of land greatly shortens the life expectation of the rabbit, but only one of the hunters bags the rabbit.
only 0.0038 mole of
TABLE
1
Direction
Volume of
solution,
liters
and moles of
acid ionized
or
formed
0.004
0.996
0.004
0.004
10
1
0.009
IS. Quantitative Expression of the Mass Law. In the above discussion of the effect of concentration on chemical equilibrium we have been content with predicting the direc-
tion of the effect of altering concentration, the qualitative
without inquiring how much a given equilibrium would be disturbed by a certain change in concentration of one or more of the reacting substances. This would be called
effect,
the quantitative
suffices in
effect.
Although the qualitative prediction

it
most
cases,
is
nevertheless often desirable to

is
make a
quantitative prediction. This
possible
by combining
182
Ch. XII
action, given in
the quantitative expression for the speed of a chemical reChapter XI, with the idea introduced in this
chapter, that at equilibrium the
two opposite reactions are
proceeding with equal velocity. For the sulfur trioxide reaction discussed above, we would have for the velocity of formation Vi = &i4o Co2 where ki is a constant. Similarly,
*
for the decomposition of the trioxide back into the dioxide oxygen, we would have for the velocity V2 = ^2^so 3
and
At
equilibrium the two velocities are equal, so that kicl 0n o2 = k 2 are constants their quotient is a &2so 3 Since ki and
-
constant,
K> so that we may write
It
is
side of the chemical equation in the numerator, those left in the denominator. This makes a large value of
customary to put the substances on the righc-hand on the
cor-
respond to a large yield. 16. By means of this expression we are able to make is qualitative as well as quantitative predictions. Since constant at a given temperature, the values of the three
concentrations must always adjust themselves accordingly. For example, suppose that it were found by measurement,
at a certain temperature, that when equilibrium was reached the concentrations were as follows: SO 2 3 moles per liter,
,
O2
mole per
liter,
SO 3
.
moles per
this
liter.
By
substituting
these values in the above expression

of the constant
From
we obtain for the value we can calculate another
set of equilibrium concentrations. Thus, if the concentration of 2 were 5 moles per liter, and that of SOa 2 moles per liter,
we would have
4
=
5
4
9
4o X
2
from which we would find the concentration of SO2 in equilibrium with sulfur trioxide and oxygen at the new concentrations to be 1.34 moles per liter.
19
183
17. It is also the
custom to denote concentrations by the
formula of the substance inclosed in brackets or parentheses. Using this notation we would write the above expression
(S0 3 )
2
K
c
(S0 2 ) (0 2 )
which has exactly the same significance as before where was used to denote concentration.
18.
the derivation of the equilibrium equation from the velocity equations in the manner just given we have ignored the fact, noted in the preceding chapter, that many reactions proceed
In
in steps, one of which may be slower than the others and hence determines the rate. Such a state of affairs does not, as might be supposed at first sight, vitiate the equilibrium equation based on the total reaction, as can be seen from the following case: the
equilibrium constant of the reaction 3
HNO = 2 NO + H O +
2 2
H+
it
+ NO - is K =
3
'
The concentration
of the
water remains practically constant in dilute solutions, therefore does not need to appear in the equilibrium equation. The velocity = fei(HNO 2 ) 3 and z; 2 = 2 (NO) 2 equations, however, are not Vi
(H+)(NO 3~),
4
2 2
for the reaction actually takes place in

2 2
HNO = N O, + 2 NO + 2 H O, which and N O + H O = HNO + H+ + NO ~,

4
is
determines the rate. There are, therefore,

right, vi
V2
= &i(HNO
2
2)
fe 2
(N 2O 4)(NO)
and and tij

v' , 2
2
v(
rium
v\
v2
and
v[
=
4
= &i(N O ), = ^(HNO,)(H+)(NO 8~). At

2
two stages, and reversible, rapid which is slow, and two rates from left to also two to the left,
equilib-
therefore
*I
h
k*
(N2
)(NO)
4
2)
(HN0
)(H )(N03"")
(HN0
*J
(N 2
4)
from which
iifti
k2 k' 2
= (NO) (H+)(N0 (HN0 )

C
3")
which is a constant, since the small fe's are all constants, identical with K, above. 19. It may be worth while to give examples of the equilibrium
equation for several other reactions.
184
Reaction
Ch. XII
Equilibrium Equation
N.
+ 3H.-2NH.
(solid)
CO Z + C
CO
is
(CO) 2
7
(UJ 2)
^r
(Since carbon is solid its concentration be expressed in the equilibrium equation.)
constant and need not
Fe 3
(solid)
+4H
Fe
(solid)
+4HO
2
^jj^ = (H
4 2)
K'
(H 20)
HC H
2
= H+ + C H 8or
2
mrm
a
(trLt^ztizDz)
HCO H CO
2
(H+XHCOQ
3
~\
;
20. Since the partial pressure of a gas is proportional to the number of molecules in a given space, and hence to the
concentration, it is possible, where gases are concerned, to write partial pressures instead of concentrations, and have constant a similar function of partial pressures. This constant
is
not necessarily the same as that where concentrations are p We would write, acused, so that we will express it as
cordingly,
^ = Kp
>
etc -
21. When a gas reacts with substances in solution it is often convenient to let the equilibrium constant express the partial pressure of the gas along with the concentrations of the dissolved substances. Ammonia gas, passed into a solution containing Ag*
24
185
+ (cf. Chapter XIII, paragraph 18) as well as gives Ag(NH 3 ) 2 and dissolved 4OH. The reaction may be considered in 3
two
NH NH NH (gas) = NH stages, = Ag(NH 2 NH (aq.) + Ag+

3 3
(aq.)
(including
NH OH)
4
3,
and
3 ) 2+.
The
equilibrium constants for
these
3,
may
2
be written, respectively, />NHS
= KI (NH
aq.)
and
Combining these gives (NH aq.) (Ag+) AS+) = Jf[Ag(NH,),+], where = K\K*. 22. In the case of carbonic acid we do not know very accurately what part of the CC>2 in solution is simply dissolved, as nitrogen dissolves, and what part is in the form of H 2 CO 3 It is not necessary
2
3 ) 2 +].
# [Ag(NH
/W
to
make
the distinction
if
we understand by (H 2 CO 3 )
of the dissolved
the
sum
of
both forms.
A similar convention should be understood for (NH 4OH)

some
in spite of the fact that consists of 3 (aq.).
ammonia
doubtless
NH
In the former case it may be convenient to relate the dissociation constant to the partial pressure of CO 2 which is proportional to CO 3 ) = K". the dissolved CO 2 so that we may write C02 /(H 2
,
Combining
this
with
K'.
(HC0
3~)/
=
C02
(H+)(HCOr)/(H 2 CO 3 ) =
we
get (H+)
Constants of Weak Electrolytes. The equilibrium constants for the dissociation of a weak electrolyte, are called dissociation constants or ionization constants, and express the strength of an acid or base in the most general way. It is evident that the stronger the electrolyte the larger are the concentrations written in the numerator of the fraction, hence the larger the dissociation constant. Instead of stating the degree of dissociation for an electrolyte at a certain
23. Dissociation
concentration, as
it is
was done
in
Chapter VIII, paragraph
13,
more
which
satisfactory to give the dissociation constant, from the degree of dissociation at any concentration may
be calculated. The values for certain familiar substances be given as shown in Table 2 on page 186, 24. The concentration of hydrogen ion in a solution of acetic acid, for example, may be calculated from the dissociation constant of the acid as follows: If the acid alone is present in the solution, the hydrogen ion and the acetate ion are at the same concentration, hence (H+) = (C 2 H 3 O 2^). Suppose that the total concentration of acetic acid is 0.1
may
186
The amount
i.e.,
Ch. XII
molar.
acid
error,
may
ionizing is so slight that the un-ionized be considered as 0.1 molar without appreciable
(HC 2 H 3
2)
0.1.
Substituting these values in
the equilibrium equation,
we obtain
1.8
10~5 and hence (H+)
0.0013.
Again, suppose that 0.05 molar acetate ion is present in the same solution, then (C 2 H 3 O 2"") = 0.05, (HC 2 H 3 O 2 ) = 0.1 and (H+) = 0.000036. It will be observed that the acidity of this solution is vastly less than that of the former.
TABLE
S
Dissociation
constant at
room
Substance
Reaction
tern-
perature*
Acetic acid
Dihydrogen phosphate ion Carbonic acidf
Hydrogen sulfide Hydrocyanic acid

Bicarbonate ion
Hydrosulfide ion hydroxide
HC H 02 H PO H CO HS HCN ~ HCO
2
Ammonium
Bisulfate ion
= = 4 2 = 2 3 = 2 = = 3 HS" = NH 4 OH = ^ HSO 4 =
8
+ CN~ + COT" + S" NH + + OH"" H+ + SO4

4
H+ H+ H+ H+ H+ H+ H+
+ C H O2~ + HPO ~ + HCO

2 3
~
1.8
6
4.3
X X X X X
HS~
4
4.7
1.8
1.2
X X
10~5 10~ 8 10~ 7 10~ 7 lO" 10 10~ u lO"" 10~ 5 10~ 2
*Ali of these values have to be increased for solutions containing high concentrations of other ions, which aid in dissociating the weak electrolyte. is 0.034 total dissolved when the partial 2 t The value of (^COa) pressure of CO* is 1 atm. at 25 C.
CO
The ionization of strong electrolytes does not obey Mass Law, for reasons suggested in Chapter VIII, paragraph 13, therefore we cannot write for them simple dis25.
the
above for weak electroHowever, that need not disturb us greatly because most of them can be considered with approximate accuracy
sociation constants like those given
lytes.
as completely ionized. It is well, however, to bear in the weak salts listed in Chapter VIII, paragraph 15.
mind
26. Solubility Product. The Mass Law can be applied to the concentrations of the ions of a sparingly soluble salt.
26
TABLE
3
187
Solubility Products*
PbBr2 AgBr
6.3 3.3
CaCO 3
Ag2 CO 3
4.8
8.2
1.7
1.7
PbQ 2
AgCl Agl
8.5
1.8
PbCr04 CaF2
Ca(OH) 2 Fe(OH) 2 Pb(OH) 2
3.4
7.9
1.6
2.8
5.5
Mg(OH) 2
Sn(OH) 2 Zn(OH) 2
*
4.5
X X X X X X X X X X X X X X X
10- 6 lO"13 10- 9 ID' 12 10-5 10-10 10- 17
CdS CuS
FeS PbS
1.4
4
1
1.0
HgS Ag2 S
SnS ZnS
3
1.0
8
4.5
-
10- 14 10- 11 10~6 10- 15 10-16 10- 12 10-26 10~ 17
CaC 2 O4 H 2O Ag2 C 2 4 BaSO4 CaSO4 2 H 2O PbSO4 Ag2 SO4
2.3
1.1
1
X KH X 1QX 10~ n X 1Q-20 X 10X 10-* X 10"29 X 10~ X K)~

8
38
63
1
24
J
2.4
1.8
1.2
X X X X X
10" 11 10" 10 10~ 5 10~ 8 10~5
The values
table in
Appendix XI
for solubility products in Table 3 are selected from the extensive of Reference Book of Inorganic Chemistry, Latimer and
Hildebrand,
New
York, The Macmillan Company, 1952.
Taking PbSO 4 as an example we write

(Pb +)(S0 4
+
)
= K.
.
10~8 Let us compute the molar solubility of PbSO 4 in pure water. Since the sole source of Pb ++ ions is the dissolved salt, the concentration of Pb ++
The value
of
at 25
C.
is
1.8
ions
is
equal to the solubility:
(Pb++)
solubility.
Likewise, the sole source of 864 ions the concentration of SO*
ions
is
is
the dissolved
salt,
so
also equal to the solubility:
(SO*
solubility.
When we combine
these relations,
2
we
find
,
(solubility}
1.8
X KT8
or the molar solubility of

If solid
PbSO 4
is,
in
pure water
PbSO 4
is
shaken with, say, 0.01
M K2SO
is 1.3
4
10"4
solution,
the concentration of
as before, equal to the soluions is now the K2SO 4 bility; but the principal source of SO 4
Pb ++
188
ions
is
Ch. XII
solution, so the concentration of SC>4
only a
:
trifle
greater than the concentration of the
K^SC^
solution
(Pb (S0 4
+)
)
solubility,
S0.01.
into
These
relations,
inserted
the
equilibrium
constant
equation, give
(solubility) (0.01)
1.8
10~8
whence the solubility of PbSO 4 in such a solution is 1.8 X lO"6 M, which is very much less than its solubility in pure water. This phenomenon is often called the ''common ion
effect/'
The
solubility product for
PbCb must
be written
whose value
If solid PbCb is dissolving in pure water, then every mole of PbCl 2 which dissolves gives one mole of Pb++ ions and two moles of Cl~ ions:
is 1.7
10~~
(Pb++)
(C1-)
= =
solubility,
solubility.
We
or,
combine these
relations, to obtain
(solubility) (2
solubility)
3
=
=
1.7
10~5 10~5
(solubility)
0.43
so the solubility of PbCl 2 is 1.63 X 10~ 2 M. (To take the cube 5 root of a number like 0.43 X 10~ it is convenient to write it
,
4.3
10"6 so that the exponent is divisible by three.) Suppose that we wish to calculate the solubility of
in 0.03
M KC1 solution. In
= (Or) =
PbCb
Pb ++
this case, the concentration of
equal to the solubility; to get the concentration of Cl" ions, we must add the chloride ion concentration arising
ions
is still
from the KC1 and that arising from the dissolved PbCl 2
(Pb++)
solubility,
0.03
+2X
solubility.
27
these
relations
189
Insertion of
into
the equilibrium constant
equation gives us
(solubility) (0.03
+ 2X
solubility)
1.7
10~ 6
To
solve this algebraic equation for the solubility is a little complicated and, unless a student comes fresh from algebra, the most feasible method is likely to be the "method of suc-
know that the solubility in this cessive approximations/' case is somewhere between zero and 0.0163, the value calculated above for PbCb in pure water. Let us assume several values as shown below and tabulate the corresponding values
for the left side of the last equation above,
We
which must be made
10~5 It to agree with the value on the right, 1.7 to approach the correct value as closely as desired.
.
is
possible
assumed
solubility
K, calculated
2.5
0.1
0.010
.001
.005
0.8
2.1
.009
.008
1.69
X X X X X
10- 5 10-6
10-5 10-6 10~ 5
27. Catalysts Do Not Shift Equilibrium. On page 169 we considered the catalyst as an agent for altering the speed must now note that in the case of reactions of a reaction.
We
which come to equilibrium the catalyst for the reaction in one direction must also be a catalyst for the reverse reaction, and that the catalyst can have no effect upon equilibrium, but only upon the speed with which it is attained. If a catalyst
could shift equilibrium, we could use a gas reaction involving a change in the number of molecules, and by alternately putting in and taking out the catalyst, which would require
little
effort,
we
could
produce an alternate increase and
decrease in pressure which could do useful work at no expense, which is contrary to the evident morality of nature. It is true that by the use of a catalyst we may reach equilib-
rium in a so much shorter time that we may be able to work at a lower temperature, where equilibrium is more favorable,
190
it
Ch.
XK
but
is
then the temperature not the catalyst which has
shifted the equilibrium.

Exercises
See Appendix II for answers

1.
following reactions can be

2
Describe experiments which would prove whether or not the made to take place in both directions:
= H + S (liquid) = Mg++ + 2 NH OH = CrO 4 (yellow) + 2 H+ = NH 4+ + Cl- + H O =

BaO
(solid)
+
4
BaO 2
2
(solid)
S;
(precipitate)
2
Mg(OH) 2
2 4
H O + Cr O ~
7
+ 2 NH
4 +;
(red)
NH OH + H+ +
C1-.
2. Hard water may be softened by means of an insoluble substance called zeolite, Na(H 6 AlSiO7), which exchanges the calcium (or magnesium) ion in the water for sodium ion as follows:
Ca++
Na(H 6AlSiO 7 )
(solid)
Na+
Ca(HeAlSiO 7 ) 2
(solid).
it
Can you suggest a way

all
of restoring the sodium zeolite after been changed to calcium or magnesium zeolite?
has
3. Describe in words the effect of adding solid sodium acetate to a solution of acetic acid, and write an equation for the reaction.
precipitation of to the equation, according

4.
The
manganese ion as manganese
sulfide,
Mn++
is
+H
(gas)
= MnS +
H+,
precipitated the precipitate?
never complete. How would you make the as great as possible? How would you redissolve
of
amount
all of
5. Write equations showing what happens when (a) 2 moles hydrogen are mixed with 4 moles of oxygen and an electric spark passed (b) dilute solutions containing respectively 1 mole of hydrochloric acid and 2 moles of sodium acetate are mixed.
;
6. Using the equilibrium constants given in Table 2, calculate the (H+) for the first five acids and the (OH~) for ammonia when the substance is present in 0.05 molal solution. 7. N O gas under certain conditions is NO On the basis of kinetic theory predict
2
2.
dissociated to give the effect of volume
change on
this reaction.
8. 0.1
191
is anthranilic acid (HC 7 6 2) 1% dissociated, + ion concentration? (b) What volume of 0.2 7V-NaOH is necessary to neutralize 50 cc. of this solution? (c) When what substances are present in the final it is neutralized by solution?
H NO
(a)
What
is
its
NaOH
9.
6
C H 5 COO- = C H COOH
water.
Explain by the kinetic theory how the equilibrium H+ should be shifted by dilution with 6 6
of
10. State in words what happens when a solution added to a saturated solution of AgAc.
NaAc
is
11. Of the following factors, which influence the solubility and which the rate of solution of a salt: (a) size of particles; (b) tempera-
ture;
(c) stirring; (d)
excess of salt?
12. If the
all
substances represented in the following equation are present in equilibrium with each other,
Cu(OH) 2
what
(d)
if
+ 4 NH = Cu(NH
3
3) 4
++
OH~,
will
be the
is
4) 2
effect
upon the amount

if
of
Cu(OH) 2
(c) if
the mixture
boiled, (b)
is
NaOH
is
added,
K SO
2
present (a)
4 is
if
added,
(NH
SO 4
added?
13. If
H+, Ac" and
HAc
are present in a solution in equilibrium,
explain, in terms of the kinetic theory, what will add (a) water, (b) NaAc solution, (c) HC1 solution.
14. If
happen
if
you
4 OH and 4+, OH-, 3 are present in water in with each other, explain in terms of the kinetic theory equilibrium
NH
(e)
NH
NH
what
(d)
will
happen
if
NaCl,
3
NH
you add
(a)
water,
(b)
NH
4 C1,
(c)
NaOH,
gas.
2
3
15. State
2
H CO + CO
16.
3
two ways
3
of shifting the equilibrium so as to decrease the amount of

of
HCOs""
HCO ~.
The amount
of
MgCO = MgO + CO
the
amount
CO
formed per second from the reaction if the CO 2 is pumped out but formed by the fermentation of sugar is not so
2 2
CO
increases
increased. Explain.
*17.
ity of
The
Agl
solubility of in 0.001
Agl
is
10~ 8 moles/liter.
What
is
the solubil-
M-KI
solution?
*18. If the degree of ionization of the

its
weak
acid
HX is 1% when
concentration is 0.1 M, what is the concentration of each substance in this solution? What is the numerical value of the ionization constant?
*
difficulty.
192
*19.
The
Ch. XII
= Ag+ OH~ 2O solubility product for Ag 2O 10- 8 and for Ag 2 CO 3 = 2 Ag+ CO 3 it is 9.0 X 10~ 12 What concentration of OH~ would be sufficient to transpose Ag 2 CO 3 ? Is the natural conceninto Ag 2 O in the presence of O.S M-CO 3
is
2.0
H + ~
tration of
OH~
in 0.5
Af-CO 3
enough to do
this?
CHAPTER
XIII
TYPES OF EQUILIBRIA
have seen, in Chapter XII, that it is possible to control reactions which come to equilibrium by changing
1.
We
the concentrations of the reacting substances. A reaction may be made more complete by using the reacting substances at greater concentration, or by removing one or more of the products of the reaction. We may now ask the questions: In what ways may substances be added to or taken away from
reacting mixtures, and what properties of substances determine whether a reaction proceeds more completely in one
answer these questions enables one, without previous experiment, to predict and control reactions in a large number of cases. It is important that the amount of experimental material to be memorized should be the minimum necessary to deal with the vast number of reactions likely to be encountered. How this material may be arranged and applied will be shown in the
direction or another?
ability to
The
following pages.
One of the properties of substances that be utilized in bringing about reactions is volatility. may If a certain reacting mixture is in an inclosed space, equilib2. Volatility.
be reached long before all of the desired products if one of the substances produced is volatile at the temperature of the reaction, it may be allowed to escape, or be pumped off, and its removal will allow more of it to be formed, according to the principle set forth in the last chapter. If this removal is continued, it may be possible to make the reaction go to completion. For example, if solu-
rium
may
are obtained but

;
sodium chloride and sulfuric acid are mixed, there is a small tendency to form hydrochloric acid, since the only
tions of
19?
19*
MANCIPLES OF CHEMISTRY
Ch. XIII
latter is a little stronger hydrogen chloride, in the
possible to produce it chloride and concentrated sulfuric acid, as follows:
than the former. However, since absence of water, is a gas, it is by the reaction between solid sodium
NaCl
If this
+ H 2 S0 4 = NaHS0 4 +
in
HC1.
were done
reached before much in this way; but if the vessel is open, so that the HC1 gas can escape, then it can all be removed, and the reaction may go to completion. Further heating, if enough salt is present, will give neutral sodium sulfate, Na 2 SO 4 the second step being
,
a closed vessel, equilibrium would be of the salt and sulfuric acid had reacted
NaCl
+ NaHSO 4 = Na SO 4 +
2
HC1.
The more
thus driven out of its salt by the less volatile one. This principle is used in the manufacture of hydrochloric acid, where the gas is caught and dissolved
volatile acid
is
number of other acids are obtained commercially by heating them with sulfuric acid in the same way, among them nitric acid, HN0 3 from the naturally occurring NaNO3 hydrofluoric acid, HF, from fluorspar,
in water.
from their
salts
from calcium acetate, 1 etc. 3. Sodium sulfate, on the other hand, may be changed to sodium phosphate by using P2 O 5 which is less volatile than
CaF2
acetic acid
SO3 The
.
reaction
3
is
Na 2 SO 4
P2 O 5 =
Na 3 PO 4
-f 3
SO3
This is a case where it may be more satisfactory to consider the salts as combinations of the metallic and nonrnetallic oxides, as explained in Chapter V. The equation is
3
Na2 O S0 3 + P2
= (Na2 0) 3 P2
it
+ 3 S0
5,
3.
Again, since Si0 2 is still less volatile than may be changed to a silicate by heating high temperature with SiO 2 as follows:
,
P2
a phosphate
to a sufficiently
(Na2 O) 3
1
P2 O 5
SiO 2
Na2 O
SiO2
P2 O 6
When wood is distilled the acetic acid is separated from the wood alcohol, acetone, etc., occurring in the distillate, by using slaked lime. Ca(OH)2, in order to convert it into the nonvolatile calcium acetate.
TYPES OF EQUILIBRIA
195
In solution, where the difference in volatility of the above substances would not be evident, the reverse changes only would take place, since silicic, phosphoric, and sulfuric acids are successively stronger, as will be explained presently.
It is well to
remember that ammonium

,
salts are easily

volatile,
,
volatilized,
and that many chlorides are rather

,
,
,
especially
4.
HgCl 2 FeCl 3 A1C1 3 SbCl 3 SbCl 5 AsCl 3 SnCl 4 Solubility. The solubilities of substances have an im,
portant bearing on the course of reactions. When a rather insoluble salt is put into water a little of it dissolves, for almost no salts are so insoluble that the amount going into solution cannot be measured. The small quantity which
does dissolve
will
be ionized, since nearly
all salts
are ionized
insofar as they will go into solution. The equation expressing the reaction when such a salt is put into water should express
this ionization, as exemplified
by the following:
BaSO 4
AgCl
(solid)
(solid)
(solid)
CaF 2
PbCrOi
(solid)
= = = =
+ SO 4 ~~", Ag+ + CP, Ca ++ + 2 F~ Pb ++ + CrO ~.

Ba++
4
When
the solution
is
saturated there will be equilibrium
between the solid salt, represented on the left side of each equation, and its ions in solution, represented on the right. The observed fact that all the above salts are only very slightly soluble means that the solutions will contain but
of their ions. It also enables us to predict that if the ions of any of the salts at any considerable concentration, they will react almost completely to form a
very
little
we mix
precipitate (from a Latin of the corresponding salt.
word meaning to throw down)
A
No
knowledge of the
solubilities
of salts, therefore, enables us to tell what ions will precipitate matter what other ions are each other from solution.
present, no matter from what compounds they are obtained, in any appreciable concentration will always Ba++ and SO 4 form a precipitate of BaSO 4 Moreover, if it is desired to " remove Ba 4 from solution most completely, our knowledge
. "
1
196
Ch. XIII
of equilibrium indicates that we should add an excess of This effect is constantly sought in quantitative SO 4
.
analysis.
5. Solution of Precipitates. Conversely, if we wish to dissolve a precipitate, we must endeavor to remove from the solution one of its ions. This removal, in the case of ions,
not so simple as is the removal of a gas, but requires a knowledge of other combinations the ion is capable of formis
ing, as we will see later. 6. Comparative Insolubility.
Which
of the
two
salts
of
ion will be precipitated depends on their relative and the relative concentrations of the ions in solubility question. If to a mixture of chloride and iodide ions is added
common
a solution of silver
ion, silver iodide, yellow, is
formed before
is
silver chloride, white.
This shows that Agl
less soluble
than AgCl, or, in other words, I" removes Ag+ from solution more completely than does Cl~ at the same concentration. This would also enable us to predict that if we start with AgCl we might bring about the following transformation
quite readily:
Agci
+r
= Ag i
cr,
whereas the reverse reaction could only be brought about by keeping the concentration of I~~ extremely small and that of Cl~ very large, as would be the case in continual washing of the Agl precipitate on a filter with a solution
of Cl".
is
it,
If,
subsequently,
we find
that
Ag 2 CO 3
silver carbonate,
readily transposed into

in
AgCl by allowing Cl" to act upon then we know that Ag2 C0 3 is more soluble than either
other words, carbonate ion,
less
of the others, or,
CO3
removes Ag+ from solution Cl" or I"", and without trying
completely than either it, we could predict with assurance that the following reaction would take place very readily as read from left to right, but not in the reverse
:
direction
Ag2 C0 3
Again, on finding
2 I"
Agl
~ + C0
3
by experiment that Agl
is
readily
changed
9 into
TYPES OF EQUILIBRIA
197
could conclude that both of the other be transposed into Ag 2 S still more easily. precipitates could It will be seen that with the aid of the ideas of equilibrium we are able to predict a large number of reactions on the basis of a few well-chosen experiments, and thus utilize
Ag 2 S by SH~, we
our experimental knowledge to the best advantage.

and products for Agl and AgCl, 8.5 X 10~ 1.7 X 10~ enable us to calculate the equilibrium constant of the reaction Agl Cl~ = AgCi I~ to be 8.5 X 1Q- 17 /1.7 X 10 7 10~ or 5 X 10~ If Agl were washed with 1 M-KC1, the maximum concentration of I~~ obtainable would be 5 X 10~7 i.e., it would require at least 2,000,000 liters of 1 M-KCl to transform 1 mole of
The
solubility
10
,
17
Agl
7.
to AgCl.
The same
and
considerations apply to relatively insoluble
acids
bases.
Magnesium hydroxide, Mg(OH) 2

2
when
put into water, dissolves slightly, forming its ions as follows:
Mg(OH) 2 = Mg++ +
Therefore
if
OH".
chloride
solutions of, say,
magnesium
and sodium
hydroxide are mixed, a precipitate of Mg(OH) 2 will be formed. 8. Since knowledge of the solubilities of salts, acids, and
bases in water is evidently extremely important in enabling one to predict and control reactions, some useful generalizations are given below. As far as the relation between solubility
ties is concerned,
and other proper-
that, other things being equal, the higher the melting point of the compound the less soluble it will be, not only in water, but in any solvent. Also, where the melting points are approximately the same, the compounds most soluble in water will be those in which there is the greatest difference in the positive and negative char-
we may note
acter of the constituent parts (cf. Chapter V), so that the salts of a metal like silver will be less soluble than those of a metal
like potassium. These the values in Table 1.
9. Generalizations
rough conclusions are illustrated by
number of statements may be made regarding the compounds of parRegarding

Solubility.
198
Ch. XIII
must be understood, however, that only the commoner compounds are considered
ticular ions such as the following. It
All nitrates are soluble. All acetates are soluble
(AgC 2 H 3 O 2 only moderately).
is
All chlorides are soluble, except AgCl, HgCl, PbCl 2 (the last sparingly soluble in cold water, moderately soluble in hot).
TABLE
1
Solubility at
20, in
moles per
Substance
WOO
Melting point
grams of solution
1.9
CaCl 2 -6H 2 O
30
185 218
H BO
3
0.077
4.3
5.5
AgNO3 NaN0 3
AgCl
KCl
BaCO3
PbSO 4 CaF2
CaSiO 3
BaSO 4
All
2
333 455 722 795 1100 1400 1510 1580
0.00001
3.3
0.0001
0.00015 0.0002
+
0.00001
sulfates are soluble,

,
except
BaSO 4 PbSO 4 (CaSO 4

,
Hg SO 4 and Ag 2 SO 4
are sparingly soluble). All carbonates and phosphates are insoluble, except those
of sodium, potassium, and phosphates are soluble, e.g.,
ammonium. [Many dihydrogen
Mg(H 2 PO 4
)2
Ca(H 2 PO 4 ) 2 and
,
Ba(H 2 P0 4 ) 2
.]
All hydroxides are insoluble, except
NaOH, KOH,
NH
OII r
aad Ba(OH) 2 Ca(OH) 2

;
sparingly soluble. except those of ammonium, sodium, potassium, magnesium, calcium, barium, and aluminum. These can be prepared as solids, but are decomposed by
is
All
sulfides
are
insoluble,
water.
All salts of sodium,
except
Na 4 Sb2 O 7 (K
, .
ammonium, and potassium are soluble, or NH 4 ) 2 PtCl 6 and (K or NH 4 ) 3 Co

,
(N0 2 ) 6
All
silver
,
salts
,
are
insoluble,
AgClO 4 AgC 2 H 3 O 2 Ag 2 SO 4
soluble).
except
last
AgN0 3 AgNO 2
,
(the
two are moderately
12
TYPES OF EQUILIBRIA
It is
199
10. Separations.
different ions present in the
upon the basis of solubilities that same solution may be separated.
Suppose, for example, that a solution contained the nitrates of silver, barium, zinc, and potassium. The addition of chloride ion, using, say, a solution of ammonium chloride,
as AgCl, which could be filtered out. The addition, then, of sulfate ion, as by using ammonium sulfate solution, would precipitate the barium
would precipitate the
silver ion
After this is filtered out, the zinc ion could be as sulfide, using ammonium sulfide. The excess precipitated of ammonium salts in the solution could finally be removed
ion as
.
BaSO 4
by evaporating the
residue,
ôlution
to
dryness and heating the
ammonium salts, leaving the potassium salts. only 11. lonization of Water. It was shown in Chapter VIII, paragraphs 19 and 20, that water is an extremely weak
which would
volatilize the
electrolyte, dissociating to a
2
minute extent as follows:
H O = H+ +
In pure water
GIT.
(OH"")
we have (H+) =
10~~
moles per
liter. This is very slight indeed, but we shall see that it is + very important. If an excess of either of the ions H or OH" is added to water, as in dissolving an acid or base in it, the result is a diminution in the concentration of the other. If,
for example, 0.001
.M-HC1
is
present, the concentration of
the hydrogen ion is increased 10,000 times, which will cause that of the hydroxide ion to decrease 10,000 times, becoming 10" 11 This inverse relationship is shown in the first two
.
columns
of Table 2.
conclude, from the slightness of the ionization of water that the reverse reaction will take
12. Neutralization.
We may
place almost completely, so that whenever an acid and a base are mixed they will react almost completely to form
water, leaving the other ions in solution, unless they happen to form an insoluble substance. We must therefore regard neutralization of acids and bases as taking place because of the fact that water is almost entirely undissociated. In
800
will return later to this topic.
Ch. XIR
connection with the neutralization of weak acids and bases
we
13. Indicators.
The concentration
of
H+
and
OH~
in a
solution
may
(cf.
indicators
be estimated approximately by the aid of page 101). Table 2 gives the concentrations of
TABLE
2
Approximate
Indicator Colors
(Abbreviations: b
blue, c
colorless,
=
*
yellow,
v =
violet, t
green, o
=
of
orange, r
red,
transition.)
pH
is
biological work. Its
an abbreviated designation of the concentration meaning is obvious from the table.
H+
much used
in
H+ and OH" between normal H+ and normal OH~, together with the corresponding colors shown by several of the common indicators. The colors given are approximate only, depending not only on hydrogen ion concentration, but also on indicator concentration, other ions, vessel size, illumination, and visual
15
TYPES OF EQUILIBRIA
Where accuracy
is
201
peculiarities.
desired, the indicator should
be used only to compare an unknown solution with one of known hydrogen ion concentration under identical conditions of the above factors.
14. lonization of
Weak
Acids, Bases,
and
Salts.
The
fact
that
many acids, bases, ionized, as set forth in Chapter VIII, furnishes other reasons
and a few
salts are
but slightly
for expecting certain reactions to take place, for the principles of equilibrium tell us that in such cases the corresponding ions will unite, when brought together, to an extent depending on the ionization of the substance. For example, because we
know that acetic acid is weak, that is, but slightly ionized, we know that when hydrochloric acid, which gives a high
concentration of H+, is mixed with sodium acetate, which gives a high concentration of C 2 3 O 2~, these ions will combine
till one or both are almost used up. Although sodium acetate is not a base, but a salt, we see that it has the effect of re-
4 OH is a weak ducing high acidity. Similarly, because base it can be prepared from any ammonium salt by the + and OH"" unite rather action of any strong base, since 4 4 +, and completely. This property is used as a test for Considerable ammonia is also in the manufacture of 3
NH
NH
.
NH
NH
given
off
is
when
coal
is distilled,
as in
making gas and coke.

in sulfuric acid,
This
extracted from the gas

.
by washing
forming (NH 4 ) 2 SO 4 When this salt is acted upon by slaked lime, Ca(OH) 2 which gives a sufficiently high concentration
,
of
OH",
there
is
set free
3 gas temperature applied into of distinguishing experimental way
NH NH
OH, which
and
H O. (We have no NH 4OH from hydrated

2
breaks up at the
NH
3 .)
It is evident, in general, that
weak
acids should
be
liberated from their salts in solution

acids,
15.
by the action of stronger and that weak bases should be liberated in like manner
by strong bases.
important application of this principle is in making "superphosphate" for fertilizer. Bones and mineral deposits contain calcium phosphate, principally as Ca 5 (PO 4 ) 3 OH, but this is so insoluble that even though finely ground it does
An
202
Ch. XIII
not furnish plants at all freely with the phosphate necessary for their growth. Accordingly the soluble calcium dihydrogen
phosphate
2
is
produced by the action of concentrated sulfuric
acid, as represented
by the equation,
2
Ca 5 (PO 4 ) 3 OH
+ 7H
SO 4 =
Ca(H 2 PO 4 ) 2
+ 7 CaSO + H O.
4 2
the
Enough lime is then added monohydrogen phosphate,

16.
to change the dihydrogen to
CaHPO 4
Successive Neutralizations.
Where the
ions of several
acids are competing for an insufficient amount of hydrogen ion, it is evident that the weakest acid will be formed first, the next weakest second, etc. In a mixture of ~ the values on page 189, Table 2, C 2 H 3 O2 and CO 3 make it evident that if H+ is added to the solution gradually, the first reaction to take place will be
,
weak
H+ + C0 3 = ~ followed by H^ + HCO 3 = ~ followed by H+ + C 2 H 3 O 2 =

17.
"
HC0 -, H CO HC H O
3
2
3, 3
2.
Complex Ions. As a
rule the positive ions in solution
are very simple, consisting nearly always only of a metallic atom, with its ionic charge or charges. There are, however,
some cases where these simple ions can unite with other ions or neutral molecules and still remain in solution as a more complex ion. They may best be considered in groups, according to the substances which are prone to form them. 18. Ammonia Complexes. A solution of ammonia in water yields all of the substances denoted in the equation,
NH + H
3
NH OH
4
NH
OH".
Ordinarily, when this solution is added to one containing an ion of a heavy metal, there is enough OH~ present to
precipitate the metallic hydroxide. If, however, more of the ammonia solution is added, the concentration of 3 will
NH
results, in the case of certain metallic ions, notably Cu++, Ni++, Co++, Cd++ y Zn++, Ag+, and Cu+, a solution which contains a complex
increase faster than that of
OH~, and there
21
TYPES OF EQUILIBRIA
203
positive ion containing both metal and ammonia. With the divalent cations the complex ions seem all to contain 4 3
NH
so that while those of the monovalent ions contain 2 3 the formulas are as follows: Cu(NH 3 ) 4 ++, Ni(NH 8 )4++ 3 is a Cd(NH3 ) 4 ++, Ag(NH 3 ) 2 +, Cu(NH 3 ) 2 +. Since the
,
NH
NH
molecule its presence does not alter the original ionic charge. In the cases of copper and nickel, these ammonia complexes are a deep blue in color, furnishing rather delicate
neutral
tests for the presence of these metals. On account of this behavior the effect of an excess of ammonia is alweiys to use up most of the free ions of these metals, with corresponding
effects
upon other
of
equilibria, as will be explained later.
The number
NHs
molecules in the complex ion can be dis-
covered by varying the equilibrium concentrations and determining which value of the exponent in Chapter XII, paragraph 22 gives uniform values of K.
19. Cyanide Complexes. Cyanide ion has the power to form complexes with a large number of metallic ions. In this
case the metals are contained in the anion as illustrated by the equation for the formation of the silver cyanide complex
ion:
Ag+
+ 2 CN- =
Ag(CN) a
(When Ag+
is first
present in any considerable amount, precipitated, dissolving in excess of CN"".)

is
AgCN
Among
Cu(CN) 2
these complexes
,
may
Fe(CN) 6 20. Complex Halides. Many

,
Zn(CN) 4 Au(CN) 2 Pt(CN) 4 ~, Fe(CN) 6 4 Ni(CN) Co(CN) 6 Co(CN) 6

,
be mentioned the following:

, .
metallic ions, especially those

halides.
of the noble metals,
have a tendency to form complex

1
This
the
particularly strong in the case of gold, platinum, and " other platinum metals/ as shown in the following:
is
AuCl 2
21.
PtCl 6 Complexes with Organic Acids. Acetate ion,

.
AuCl 4
ion,
C2H 3 (V~,
oxalate
CeHsOr form complexes with some ion, C 4 H 4 Oe example is Fe(C2O 4 ) 3

,
C2O 4
,
citrate
ion,
and tartratc
metallic ions.
An
204
between the Foregoing Factors,
Ch. XIII
22. Competition
We
have
seen, in a few instances,
how
reactions are determined
by
competition between the various ions of weak acids, or the relative solubilities of various salts of the same ion. We are now prepared to discuss competition between the different
factors, volatility, solubility, ionization of water,
weak
acids,
bases and
salts,
complex
ions,
and to consider general examples
of the control of reactions.
When the salt of a weak acid is dissolved water we have present in the solution an ion that has a great tendency to combine with hydrogen ion. Now water, though it is such a weak electrolyte, yields some hydrogen ion. Consequently, there is a slight formation of the weak acid, with a resulting decrease in the concentration of the hydrogen ion and a corresponding increase in the concentra23. Hydrolysis.
in
tion of the hydroxide ion. To say this concretely, let us consider a solution of sodium acetate, which gives a large concentration of Na+ and C 2 3 2 ~. Now, since the water yields a
HO
trace of
acid, liberating an excess of OH~, so that the solution will be slightly alkaline. This may be expressed by an equation as follows:
there
H+ and OH", and since HC 2 H 3 O 2 is a weak will be some union of H+ and C 2 H 3 O 2 to form the
~~
acid,
C2 H3
It will
+H
= HC 2 H 3
OHT.
be observed that this reaction is the reverse of the neutralization of acetic acid with a strong base, and since the latter reaction is nearly complete, of course the former can take place but slightly under similar conditions.
In writing the equation we show the net effect of what has happened, as expressed previously in words. We must guard against the error of thinking that the formulas on
the right-hand side of the equation tell what is in the solution after equilibrium is reached. The solution still contains ~ 2 O, which fact is expressed by saying mostly C 2 3 O2 and that the above substances react only slightly before equilibrium is reached, not by writing their formulas on both sides
of the equation. Moreover, in a single equation like this,
we
24
TYPES OF EQUILIBRIA
205
should not write water as ionized, for the bulk of it is unionized. As a matter of fact, there are two simultaneous
reactions occurring, as follows :
C 2 H 3 O2
+ H+ = HC 2 H
2,
and
H 2 O = H+ +
OH".
two gives the former. ~~ there is a competition between C 2 3 O 2 and Obviously OH" for the H+, as might be represented in this way ~
of these
The sum
HC 2 H 3
= C 2 H3
+ H+ +
II
OH"
H 2 0.
OH" should get or keep most of the H+ is to be from the fact that water is vastly less ionized than expected is acetic acid. It is this disparity between the ionization of ~ the two substances that enables C 2 H 3 O 2 to set free but a slight amount of OH" from water, on the one hand, and which causes neutralization of HC 2 H 3 O 2 by OH" to be nearly complete, on the other hand. 24. If, instead of an acetate, we dissolve in the water the salt of some weaker acid, like sodium phenolate, NaOCeH 5 we have in phenolate ion, OC 6 H 5 ~, one which will unite with the hydrogen ion of water more completely than will acetate
That the
,
ion,
forming
HOC H
6
5,
the acid
known
as phenol, or carbolic
and setting free from the water more OH~ than in the case of sodium acetate. The competition for H+ is here between OH~ and OC 6 H 5~, and though the latter gets but little of it, since carbolic acid is much more ionized than water, it nevertheless gets more than does acetate ion. We may express this competition in the same manner as before,
acid,
HOC H = OC 6 H
6
5
~
5
+ H+ +
OH"
II
H 2 0.
206
net result
Ch. XIII
The
we may
write, as before,
~ OC 6 H 5 + H 2
HOC H +
6 5
GIT.
process such as this is called hydrolysis. The idea underlying the name is that a salt is split up by water into free
acids always hydrolize in aqueous solution on account of the possibility of forming the free weak acid. Of course, the ions giving weak bases also take part in hydrolysis. All ammonium salts are hydrolyzed, because of the formation of the weak base, hydroxide, as illustrated by the equation,
acid and base.
We
see that salts of
weak
ammonium
NH + + H
4
NH OH +
4
H+,
where the solution becomes slightly acid. If the salt is one of both a weak acid and a weak base, like ammonium acetate, NH 4 C 2 H 3 O 2 both of its ions take part in hydrolysis, as shown by the equation,
,
NH + + C H
4
2
+ H O = NH OH + HC H O
2
2.
In a case like this the acidity or alkalinity of the resulting solution depends upon whether the acid or the base is weaker.
In this particular case they are of almost identical strength, may be seen from the values in Table 2, page 190, so that the solution is almost neutral, though it does contain more
as
NH OH
4
than a solution of
NH
4 C1,
and more
free
HC 2 H O
3
than one of
in splitting
NaC 2 H 3 O 2
since both of the ions present aid
An
it,
up the water. + is to consider alternate point of view regarding 4 + = 4 itself, as a weak acid, dissociating as follows:
NH
NH
H+. This has certain advantages in simplicity of 3 representation, although it is not essentially different from + + H 2O = 4 4 OH 3 and H+ are H+, for both
NH +
NH
NH
NH
"hydrated."
25. Applications of Hydrolysis. Hydrolysis plays an important part in many reactions, a few examples of which will be given. It is desirable that solutions to be used for house-
hold cleaning should have a slightly alkaline reaction, since
$26
TYPES OF EQUILIBRIA
and removing
dirt,
207
this aids in emulsifying grease
and also
tends to soften hard water, as will be explained later. It is not desirable, however, to use a strong base like sodium hydroxide, because this gives too great a concentration of
OH~, which has
fabrics, unless used in
injurious effects on the hands and on some very dilute solution, where the slight
amount of OH" would soon be used up. What is wanted is a solution containing but little free OH~, but which is able to yield .more should this be used up. Such is the case with
ammonia,
so that
it
finds large use in the

fulfill
home.
We
see also
these conditions, and several of them find extensive application as cleansing agents. Sodium carbonate, Na 2 CO3 is the salt of a very weak acid,
that salts of
weak
acids
and
its
:
solutions give a very
marked
alkaline reaction, as
follows
C0 8
On
this account
it is
+H
= HC0 3 "
OH".
as 'washing
'
extensively
known and used
soda."
NaHCO
There are two sodium carbonates, this one and sodium acid carbonate. The solution of the latter 3
,
also undergoes hydrolysis,
However,
3
HCO " + H 2 O = H 2 CO + OH~. since H CO is considerably more dissociated

3
than
HCO ~, according to the figures given on page 190, the former ~ and H+ less completely than the will be formed from HCO
3
and H+. Hence the solution of NaHCO 3 and " whereas the latter is used only is used as washing soda," where a much less alkaline reaction is desired, as for internal use. The NaHC0 3 on the other hand, is "baking soda," because it can yield much more CO 2 for the same weight both of itself and acid. 26. Borax, sodium borate, is the salt of the very weak boric acid, and has the same effect in cleansing as sodium carbonate. Sodium silicate, the salt of weak silicic acid, behaves in the same way, and is a constituent of laundry soaps.
latter will
be from
CO 3
Na 2 CO 3
is
much more
alkaline than one of
208
27.
Aluminum
.
Ch. XIII
Al +++ and ferric ion, Fe+ ++ are partially hydrolyzed to ions such as A1OH++ A1(OH) 2 +, FeOH++ and Fe(OH) 2 + The hydrogen ion liberated by the hydrolysis causes the solution to become distinctly acid. If the ion of a
ion,
, ,
very weak acid
added, the hydrolysis is complete, yielding A1(OH)3 or Fe(OH)3 and the weak acid. For example, aluminum salts can be used to liberate carbon dioxide from carbonates,
is
as
is
done
in the
alum baking powders:
A1+++
+ 3 HCO 3
= A1(OH) 3
+ 3 CO
'
2.
The foam type

or petroleum
solution and
of
fire
fires
on
oil
extinguisher, for extinguishing gasoline tanks, makes use of sodium carbonate

sulfate solution, with the addition of a
aluminum
foam
28.
stabilizing agent such as glue. When a sparingly soluble salt of
a very weak acid
dis-
solves in water, the anion undergoes hydrolysis. For example,
CaC0 3 + H 2 O = Ca++ + HCO 3 - + OH~, ZnS + H 2 = Zn++ + HS~ + OH~.

There are a number of other compounds, such as the chlorides of the nonmetals, that undergo complete hydrolysis. When PCls, phosphorus trichloride, is put into water the
29.
following reaction takes place
PC1 3
+ 3HO
2
= P(OH) 3
+ 3 H+ +
3 C1-.
The hydroxide
phosphorus is so completely an acid rather than a base that the above reaction is complete. 30. Choice of Indicator. In titrating a weak acid with a
of
when
will
strong base, or vice versa, it is necessary to determine, not the solution is neutral, but when it contains equivalent
amounts
be
of acid
free,
may
be. If
and base, a minute proportion of which giving an alkaline or acid reaction, as the case sodium acetate, for example, is dissolved in water,
is
the solution
of acid and base are present.
slightly alkaline, although equivalent amounts To reproduce this condition,
31
TYPES OF EQUILIBRIA
209
when acetic acid is titrated with sodium hydroxide, one should use an indicator like phenolphthalein, which, as shown on page 200, changes color in a solution which is faintly
alkaline, so that a slight excess of either acid or base would affect the indicator. Similarly, in titrating ammonia with
hydrochloric acid, we wish to end with the solution not really neutral but slightly acid, since a solution of ammonium
chloride reacts slightly acid. Hence an indicator like methyl orange, according to the table on page 200, would be suitable
for this purpose. In general, the proper indicator to use in
titration
result
may be found by taking the normal salt which will from the titration, dissolving it in water and determining what indicator will change color when a drop of solution of the free acid or base is added in excess. 31. The Solution of Hydroxides. We have seen that when a more or less insoluble metallic hydroxide is in contact with water it gives to the water a certain amount of its ions,
equilibrium being reached the sooner the less soluble the hydroxide. As an example we may consider magnesium
hydroxide, Mg(OH) 2 ions as follows:
which gives a small concentration of
Mg(OH) 2 = Mg++
OH".
We have seen also that hydrogen ion has a very great tendency
to unite with hydroxide ion. If, therefore, H+ is added to the precipitate of magnesium hydroxide suspended in water, there will be a competition between the H+ and the Mg++
for the OH~~,
which
may
be represented, as before, by the
double equation,
Mg(OH) 2 = Mg++
+ 2 OH~ +
2H+
II
2H O.
2
Now,
since water
is
so extremely undissociated
we might
210
PRINCIPLES OF CHEMIS1RY
Ch. XIII
expect that the H+ added would be successful in stealing the OH" away from the magnesium ion, liberating the latter, which would thus go into solution so that the effect of the acid would be to dissolve the precipitate. The total reaction
is
therefore
Mg(OH) 2
As a matter
ions that
it
+ 2 H+ =
Mg++
+2H
2 O.
of fact, water is formed so completely from its takes but a moderate concentration of acid to
dissolve practically all hydroxides. Our principles of equilibrium
would lead us to expect that any substance that would unite with OH" would have the effect of dissolving insoluble bases. Besides H+, we have found that NH 4 + is a substance which has a tendency to unite with OH~ to form the weak base NH 4 OH. We know, however, that these two ions do not unite nearly so completely as do H+ and OH", therefore we should not expect
NH
is
+ to be nearly as effective as H+ in dissolving bases. It true that the solubility of any base will be increased by
4
the presence of 4 +, but if the base is very insoluble to begin with, the increase may not be sufficient to bring the amount in solution up to a value such that we would call it
soluble. Suppose, for example, that the solubilities of two bases in water are 0.001 and 0.000,001 molal respectively, + is and that the addition of a certain amount of 4 enough
NH
NH
to increase each 1000 times. The effect would be to make the solubilities of the two bases now 1 molal and 0.001 molal, 4 +, respectively. We would then call the first soluble in
NH
but the second, insoluble. Among the insoluble bases which may be thus dissolved in NH 4+ are Mg(OH) 2 Ca(OH) 2
,
Zn(OH) 2 Fe(OH) 2 Mn(OH) 2 Ni(OH) 2 Co(OH) 2 32. The Solution of Oxides. Oxides of metals are much
, ,
, ,
like the corresponding hydroxides, and may either be converted into hydroxides, in some cases, or produced from them by heating. The solubility of hydroxides in H+ leads us to expect that oxides will likewise dissolve in acids. We
may
think here of the formation of water from the
H+
of
33
TYPES OF EQUILIBRIA
211
the acid and the oxygen of the oxide. Most oxides, indeed, are easily dissolved in acids, though more difficultly than are the corresponding hydroxides. This difficultly may be largely a matter of the speed of the reaction. In a few instances, notably Fe 2 Oa, Cr2 Oa, and Al 2 Oa, heated to a very high temperature they insoluble in acids.
if
they have been

practically
become
33. Amphoterics. There are several metallic hydroxides that are capable of acting either as weak bases or weak acids. Any substances that behave in this way are called amphoteric.
Such a substance
cation and the
anion.
may
give to water not only the metallic
OH~ of a base,
Taking Pb(OH) 2
but also H + and a corresponding as an example, we may express this
double power of dissociating as follows:
Pb++
+ 2 OH- =
Pb(OH) 2 = H+
+ HPbO ~.
2
From the double equilibrium that we have represented it will be seen that the precipitate can be dissolved not only by the + which would act as follows: addition of
Pb(OH) 2
+ 2 H+
= Pb ++
+ 2H
O,
but also by the addition of OH~, which would act in the following way,
Pb(OH) 2
+ OH- = HPbO ~ + H O.
2
2
It is possible, therefore, to have lead present either in an alkaline or in an acid solution, while in a solution approxi-
mately neutral
it
cannot
exist,
but will be precipitated as
Pb(OH) 2
Other hydroxides behaving in this way are those of zinc, chromium, aluminum, and tin (both stannous and stannic). This amphoteric character may be made use of in separating from each other metallic ions existing in the same solution. " 4 4 4 Thus Fe 4 is commonly separated from Al and Cr4 4 4 by adding concentrated OH~ in excess, which leaves the first
"""
"
"
"
"
"
"
212
Ch. Xht
precipitated as Fe(OH)a, but dissolves the others as aluminate and chromite ions respectively.
There are many substances in addition to the hydroxides mentioned above which are amphoteric. The most important are the amino acids, which are the units out of which proteins
34.
are built
is
(cf.
Chapter XVIII, paragraph
21).
One
of these
2 2 2 COOH. The glycine, amino-acetic acid, towards at one end of the molecule, can react like 3 group, + can water, liberating OH~, while the split off from the
NH CH
H
NH
NH
other end. This substance can accordingly neutralize either H+ or OH-.
weak polybasic acids may be as amphoteric, since they are able to react with regarded either H+ or OH~. In this category are 2 PO 4~, and 3~,
intermediate ions of
The
HCO
35. The isoelectric point is the hydrogen ion concentration at which an amphoteric substance is least ionized in both directions. If it is a relatively insoluble substance, its solubility
would be at a minimum at that point.

.
If its
acid
and
basic strengths are equal, then the isoelectric point is at 7 If its acid strength is greater than (H+) = (OH") = 10~
basic strength, a higher concentration of H+ is necessary to repress the acid ionization and the isoelectric point will
its
be at (H+)
In
point
of
>
10- 7
the
is
case
of
glycine,
at
pH
6.1, or (H+)
paragraph 34, the isoelectric 7 7.5 X 10" The proteins, built

.
amino acids, have their characteristic isoelectric points, up at which they do not migrate in an electric field, where they show the least swelling or, if in colloidal solution, the maximum
viscosity.
The
following isoelectric points are illustrations:
gelatin, 4.7; egg
albumen, 4.8;
4.
insulin, 5.4;
hemoglobin, 6.8;
Ion.
pepsin, 3; wool, 36. The Solution of Sulfides in

larity
Hydrogen
The
simi-
has been previously pointed out, also the fact that hydrogen sulfide is a very weak electrolyte, like water. It is but a slight transition, therefore, from the consideration of oxides to that of sulfides. The chief
sulfides
between oxides and
37
TYPES OF EQUILIBRIA
is
213
difference to be noted
that whereas reactions like the
following are very numerous,

Zn-H-
+ 2OHT =
Zn(OH) 2
the corresponding reaction, when sulfur is substituted for oxygen, is the formation of a sulfide, rather than a hydrosulfide, as
shown by the
Zn++
reaction:
SIT = ZnS
+H
2 S.
This
of
is
,
Ag+
and,
analogous to what takes place with OH"" in the case when the solution is boiled, with CU++, as shown
2
by
Ag+
+ 2 OH" =
Ag2
+H
O,
and
Cu++
+ 2 OH~ = CuO + H
H
O.
The
moval
solution of a sulfide in an acid depends upon the reof the sulfide ion by the hydrogen ion of the acid to
sulfide,
2 S,
form hydrogen
and
its
precipitation depends
upon the presence of sufficient sulfide ion. This competition between the metallic ion and the hydrogen ion for the sulfide
ion
may
be represented by the scheme used before,
ZnS = Zn++
+
2H+
II
H
37.
finds
2 S.
Some
enough
sulfides are so insoluble that the metallic ion
sulfide ion to be precipitated
even when the
solution
contains a moderately concentrated acid. These sulfides, conversely, will not be dissolved by hydrogen ion in moderate concentrations. The sulfides which behave in this way include Ag 2 S, HgS, PbS, Bi 2 S3 CuS, As2 S 3 As2 S 5
, , .
Next,
,
we have
dilute.
several,
including CdS, Sb2 S3

if
SnS2 that
if it is
will dissolve
the
H+
is
Sb 2 S 5 SnS, concentrated but not

, ,
Then
follow ZnS,
MnS, FeS, NiS, CoS, which
214
Ch. XIII
are so soluble that dilute precipitation. The cases of
H+
is
sufficient to
NiS and CoS
prevent their are peculiar in that
they are not precipitated in acid solution, but nevertheless will not dissolve at all rapidly in dilute acid if first precipitated from an alkaline solution. This may be due to the existence
of
two modifications
modification
of the solids, so that

is
when the more

it
changes over be an example of slow rate of reaction, similar to the slow reaction between certain acids and oxides, referred to in paragraph 32. In
soluble
into the insoluble modification; or
it
once precipitated
may
order to precipitate this group of sulfides it is necessary to have a neutral or slightly alkaline solution so that sufficient sulfide ion can be present. The usual reagent is a solution of
"ammonium
"
sulfide,
made by
passing
H 2 S into NH 4 OH soluby adding acetate
tion. If acetic acid is used, it is possible,
+ sufficiently to allow ion, to reduce the concentration of the precipitation of ZnS. 38. Another factor that may be used to assist the solution
of a sulfide is the volatility of
2 S.
If
the solution
is
boiled,
the
H2S
is
more
readily removed, so that more can form,
resulting in an easier and more rapid solution of the sulfide. To dissolve the less soluble sulfides the use of concentrated
H+, together with boiling the solution, is insufficient, and we that it is necessary to destroy the Chapter H 2 S by an oxidizing agent. The order of solubility of the above sulfides in water is roughly as follows, beginning with the most soluble: MnS, FeS, ZnS, NiS, CoS, SnS2 SnS, Sb 2 S 3 CdS, PbS, Bi 2 S 3
shall see in
XV
CuS,
As 2 S 5 HgS. Ag 39. Amphoteric and Acid

2 S,
,
Sulfides.
We
have seen how
several hydroxides are able to dissolve in OH". There are, likewise, five sulfides which can dissolve in either OH"" or
SH~, namely, As2 S 3 As2 S5, Sb 2 S3 Sb 2 S 5 SnS 2 The analogy between the oxides and sulfides may be brought
,
out in the following parallel reactions:
As2 O 5 + 2 OH" = As2 S 5 + 2 SB" =
2 2
AsO-f
AsS-f
+ H 2 O; + H2 S.
41
TYPES OF EQUILIBRIA
dissolved in
215
The oxide may be

ions.
SH~ and the sulfide in OH"" the above products or else intermediate to produce mixtures of
The compounds in which the metals have the lower number are always less acidic, both in the case
oxidaof the
tion
oxides and the sulfides, hence

difficulty in
ammonium
sulfide,
Sb 2 S 3 dissolves with some and SnS is practically in-
In dissolving both of these sulfides ammonium sulfide is used, which contains polysulfide yellow etc. Although these ions are usually ions, such as S 2 ~~~, S 3 in this way for the sake of simplicity, they are actually written
soluble in the same.
,
ions of
weak
acids and
~~,
it
would be doubtless more accurate
to write:
HS2 ~, HS3
all
etc.
They
three metals, changing ion of the higher oxidation number, thus,
lower sulfides of
are capable of dissolving the them to the sulfo-
Sb 2 S 3 SnS
40.
of
+S +S
~~
3
= 2 = SnS 3
The extremely
insoluble
HgS
will dissolve in
a solution
Na2 S,
according to the reaction:
HgS
but
will
= HgS,
"ammonium
SH~,
not dissolve in
sulfide/'
which conshifts
tains
chiefly
equilibrium S
by forming
solution.
NH
is
NH + and +HO =
4
2
because
NH
+ 4
the
SH~
+ OH"
little
so far to the right,

exists in the latter
OH,
that very
When
the
acid
added to the solutions of the above sulfo-ions
produced, reprecipitating the sulfides, just as the addition of acid to stannate ion reprecipitates the stannic hydroxide. This reprecipitation consists simply in the reversal of the reactions whereby these sulfo-ions are
acid,
2 S, is
weak
produced.
41. Separations.
The
different behaviors of sulfides
towards
the
is made the basis of important separations in both qualitative and quantitative analysis. If a solu-
H+ and SH~ or S 2
216
Ch. XIII
tion contains the following ions, Pb++, Bi+++, Cu++, AS+++, can be divided into Sb+++, Sn++, Zn++, Mn++, Mg++, they substances controlling the concentrations of the
groups by
in the equilibrium,
H 2 S = H+ +
All ions
SET =
H+
S~.
This separation can best be outlined by the aid of a diagram.
Acids. Salts of all weak acids the addition of H+. This increase by in solubility, in the case of carbonates, is enough to bring all insoluble carbonates into solution in dilute H+. A very interesting case of the solution of a carbonate was alluded
42. Salts of
Other
Weak
are
made more
soluble
to in Chapter XII, paragraph 2. It
is
the reaction whereby
hard water
produced from limestone rock. If very dilute as is present in very dilute HC1, is allowed to act upon H+, CaCO3 the CO 3 which the latter gives to the solution
is
,
very slight amount is converted into HCO 3 only, and not into H 2 CO 3 as would be the case if more concentrated acid were used. The equation for this reaction is as
in
,
"
follows
CaCO 3
+ H+ =
HCO 3-.
44
If
TYPES OF EQUILIBRIA
3 is
217
H 2 CO
H+
used instead of HCl, it also can furnish sufficient to bring about essentially the same reaction,
CaC03 + H 2 C0 3 =
Ca++
+ 2 HCO ~.
3
Since most surface water contains some dissolved carbon dioxide, the above reaction takes place whenever such water flows over limestone. A quite analogous reaction occurs with MgCO3 The reaction can be reversed by removing the
.
either by boiling the solution, as occurs in a teawhence the name "temporary hardness/' or else by kettle, neutralizing it with some alkali, or some substance giving OH~ by hydrolysis, like sodium carbonate or borax. When this is done on a large scale, the water is analyzed and just the right amount of Ca(OH) 2 is added. Although more Ca4" is added in this way, there is produced enough CO 3
2 3,
"
1
H CO
to precipitate the equation:
all
of
it;
the total reaction
is
represented by
Ca++
+ HCO - + OH- = CaC0 + H O.

3 3
2
When
a
the hardness in water
is
salt like CaSO-i, it is necessary to
produced by dissolving add CO 3 (as Na2 C0 3 )
to precipitate the
43. Basic
Ca++ Salts. When

.
well.
formed may This is the case with the carbonates of copper, lead, and mercury, as illustrated by Pb(OH) 2 2 PbCO 3 the "white lead" of the painter. Mercurous and mercuric nitrates readily form basic nitrates. The addition of hydroxide to ferric acetate
,
hydroxides are precipitated, the solid be a definite compound containing other anions as
or sulfate precipitates basic ferric acetate or sulfate. 44. Solution of Phosphates. There are no phosphates so insoluble in water but that they are dissolved by moderately
concentrated H+. Although PC>4

acid,
is
HPO 4
all
nevertheless dilute
H+
the ion of the very weak is not sufficient to
normal phosphates, both because some are so insoluble to begin with that the increase is not sufficient to make them soluble in the usual sense, and also
dissolve
of the
S18
Ch. XIII
because some monohydrogen phosphates, like CaHPO 4 are rather insoluble, and even though Ca 3 (PO4)2 be converted into the former, solution does not result. As a rule the acid salts are more soluble than the normal
,
salts,
as exemplified
is
by the
series of
is
calcium phosphates.
Ca(H 2 PO 4 ) 2
is
soluble,
in
CaHPO 4
The
very insoluble
water.
insoluble, and Ca 3 (PO 4 ) 2 chief exception to this rule is

is
furnished by the sodium carbonates, where the acid salt the less soluble.
45. The industrial preparation of sodium carbonate by the Solvay process furnishes an interesting application of the principles here discussed. The normal salt, Na2 CO 3 is very soluble, but the acid salt, NaHCO3 is not very soluble in the cold. The latter can therefore be precipitated by ~ + and in sufficient 3 bringing together the ions Na
, ,
HCO
concentration.
To do
this,
NH
gas and
CO 2
into a cold concentrated solution of NaCl.
The
gas are led acid and
base produced by the solution of the gases in water react + and 4 3 ~, provided they are used in the ~ and when the concentration of HCO 3 right proportion,
to give
NH
HCO
reaches a sufficient value it begins to precipitate the Na+ as NaHCO 3 (cf. Chapter XXI, paragraph 17). 46. Solution by Forming Weak Salts. In the previous cases
compounds which could be brought into solution by adding some substance, especially H+, which would use up the anion of the precipitate. It is likewise possible to dissolve a compound by adding some reagent that will use up the free cation. CdI 2 for example, is a moderately weak salt, consequently the following reaction can be made to proceed to some extent by using a sufficient contreated
,
we have
centration of
I"":
CdS
2 I-
+HO =
2
CdI 2
+ HS- +
Ions.
OH-.
Wherever the
47. Solution
by Forming Complex
cation
capable of forming a complex ion, a precipitate can rendered more soluble than it is in water. Thus, a salt be
is
like
ZnCO 3
can be dissolved, not only by using up the amen,
48
TYPES OF EQUILIBRIA
219
as in adding H+, but also by using up the cation, as when Zn(NH 3 ) 4++ is formed by the addition of ammonia solution.
The competition between

represented as before
:
the
CO3
and the JNH 3
may
be
ZnCO 3 =
Zn++
~" + CO
8
4NH
II
Zn(NH 3 ) 4 ++.
the concentration of the ammonia is sufficient, the complex is formed at the expense of the insoluble carbonate, resulting in the net reaction,
If
ion
ZnC0 3 +
It is
NH
= Zn(NH 3 ) 4 ++
+ CO,.
in
worth noting that the solution of Zn(OH) 2

the reaction:
NH
(aq.),
by
Zn(OH) 2
+ 4 NH = Zn(NH
3
3)4
++
+ 2 OH"
would be assisted by
NH
4 +,
if
present, reacting with the
OH~, giving a net reaction of:
Zn(OH) 2
+ 2 NH + 2 NH 4+ = Zn(NH
3
3) 4
++
+ 2 H O.
2
In the case of ZnS, which is much less soluble, the formation of the complex ion cannot take place to an appreciable extent, so that ZnS is not dissolved by ammonia. The copper
ion seems to be formed more completely than the corresponding zinc ion, so that traces of Cu(NH 3 ) 4 ++ can be formed from CuS if concentrated ammonia is used, in spite of the smaller solubility of CuS. 48. Solution by Forming Ions of Amphoteric Hydroxides. The effect cf a considerable concentration of OH~ may be
ammonia complex
to dissolve the relatively insoluble salts of certain metals, in a fashion similar to that whereby complex ions are formed. In fact, these ions may be considered as complex ions. Most
220
Ch. XIII
of the lead salts, for example, are dissolved exemplified by the reaction,
by OHT, as
PbSO 4
+ 3 OH"
H2 O + HPbO2~ + SO 4
Even ZnS is not so insoluble but that it can be dissolved by concentrated OH". 49. Systematizing the Reactions of a Given Ion. It is not
necessary to perform and remember all of the reactions of a certain ion with a set of reagents in order to tell what they
will be. It suffices to
make an
intelligent selection of
a few
of the possible reactions and arrange the resulting information systematically. As an example of what is meant let us
consider a
number
of the reactions of silver fon, Ag+, with
the following: CO 3 ", OH~, CN~, CP, Br~, F, NH 3 Let us assume that we have performed experiments S2O3 which show that the reactions take place which are represented
S,
by the following equations
as read from left to right :
+ Br~ 2 NH Ag(NH + + r Ag2 O + H 2 + 2 CP Agl + 2 CIT Ag2 CO3 + 2 OH~

AgCl AgCl +
3
3)2
= = = = = =
AgBr
CP,
)2
+ CP, + 2 NH Agl 2 AgCl + 2 OH", Ag(CN) + r, ~ Ag O + H O + C0

Ag(NH 3
3,
(easily
re-
AgBr
S2
Ag(S2 O3
= )2 CN" = AgCl + Ag(NH 3 ) 2+ + Br~ = 2 Ag(CN)r + ST- = Ag2 C03 + 2 CP = AgCN + 2 NH 3 =

list
+r
~ = Ag(S
Agl
versed)
2 3 )2
S2 O 3
+ " Br~,
,
AgCN +
AgBr
2
CP,
3
+ 2 NH
3 3)2
(easily reversed)
N
~ + C0 Ag(NH + + CN~.
AgCl
A g2 S +
4 CN-,
From
these observations
following ness with which they unite with Ag+ to form a precipitate or a complex ion as the case may be. It must be understood
it is possible to arrange the of substances in the order showing the complete-
50
TYPES OF EQUILIBRIA
221
that the reagents forming complexes are taken in moderate

excess:
Reagent
To form
CO 3
OH""
CP
CIsT
Ag 2 CO3 Ag2
AgCl
NH
AgCN
AgBr
Ag(S 2
Ag(NH 3 ) 2 +
3) 2
r CN" S~
SO. In order to
Br" S2 3
Agi
Ag(CN)r
Ag2 S
make
this
list
it
is
necessary to
it is
make
possible to predict the direction of forty-five reactions. The list was made in such a way that each substance in the first
will steal Ag+ away from its combinations with any substance above it, because less Ag+ can exist in the same solution with substances farther down the column than with those higher up at the same concentration. Thus + AgBr gives to the solution more Ag than can exist together
minimum
of nine observations,
and from them
column
with
I",
hence the following reaction
will readily
take place:
AgBr
+r=
Agi
Br".
For the same reason, Agi will dissolve in CN~~, and also any precipitate in the above list can be transposed into Agi by I" except Ag 2 S. Where two substances have about the same power to combine with Ag+, as is the case with NH 3 andl Br"", it is possible to reverse the reaction easily by altering
the concentrations.
Thus the
2
3
reaction,
AgBr can be made to take

right to
left,
+ NH
= Ag(NH 3 ) 2+
Br~,
place as read from left to right or from
3 or that according as the concentration of of Br"", respectively, is taken in sufficient excess. By adding to the information given by the above list a few facts about the other reactions of the substances, we
NH
are able to predict a very large
number
of reactions.
For
222
Ch. XIU
a very weak acid, hence AgCN can be dissolved by H+. For the same reason, H+ will liberate Ag+ from a solution of Ag(CN) 2~, and if Cl~ is present along with the H+, then AgCl will be precipitated as follows: example,
is
HCN
Ag(CN) 2
H+
Cl"
In similar fashion, AgCl will be 3 ing to the reaction represented earlier, but will be reprecipitated on the addition of H+, which takes up the 3 to form the Ag+ to recombine with the Cl" left from 4+, allowing
,
+ 2 HCN. dissolved by NH accord-
= AgCl
NH
NH
the previous reaction, as shown by the equation: + 2 2 H+ Cl~ = 3 2
Ag(NH
AgCl
+ NH 4+.
Again, since Ag2 SO 4 is moderately soluble (cf. paragraph 9), we see that it can be readily transposed to AgCl by dissolving it in water and adding Cl~~, for AgCl is insoluble. In order to reverse this transposition we see that some other
principle besides solubility
must be invoked.
,
If
water
is
absent, HC1 as
we can
2
compared with
take advantage of the greater volatility of H 2 SO 4 so that the reaction,
AgCl
+H
S0 4 = Ag 2 SO 4
HC1,
can be brought about by heating AgCl with concentrated
H 2 SO 4
general applica* tion of the above principles and information can be illustrated by further miscellaneous examples.
51. Miscellaneous Transformations.
The
To change CaSO 4
to
CaCO 3 we
can take advantage of the
greater solubility of the former (cf. paragraph 9) it with a solution of a soluble carbonate, like Na 2
gives
and treat CO3 which

,
be precipitated. The manner of expressing this in an equation would depend upon whether the amount of water present is such that the
,
C03
when
the insoluble
CaCO 3 would
CaSO 4 is mainly present as solid or as dissolved ions. These cases would be represented respectively as follows
CaSO 4
Ca^+
+ CO " = CaCO
8
3
.
SO 4
+ CO
= CaCO 3
53
TYPES OF EQUILIBRIA
223
to
To bring about the reverse transformation we would have make up for the greater solubility of CaSO 4 which shifts
,
,
the equilibrium towards CaCO 3 by adding H+, which use up and reverse the reaction. 3
would
CO
52.
To change CuSO 4
by
Cl~.
to
CuCl 2
it
is
necessary to replace
SO 4
This might be done by adding BaCl 2 to a
solution of the
CuSO 4
SO 4
giving the reaction,
Ba++ = BaSO 4
of BaCl 2 were used, all of the would precipitate each other, leaving present in solution Cu++ and Cl~, and if the precipitate were filtered out and the solution evaporated, these ions would combine to give solid CuCl 2 as desired. However, it is difficult to add just the equivalent amount of BaCl 2 and it is accordingly better to use a different method, with reagents an excess of which can be easily removed. Since Cu(OH) 2 is insoluble, it can be precipitated by adding OH~ (e.g., NaOH solution)
If
exactly the right
amount
Ba++ and
SO 4
to the solution of
out, the
CuSO 4
If
the precipitate
is
now
filtered
SO 4
can
now be
disposed dissolved by HC1
is
of.
precipitate of Cu(OH) 2 solution, since the H+ of the
The
H evaporated, go with the water as HC1 gas, leaving finally solid CuCl 2 along By precipitating the carbonate, instead of the hydroxide, the same transformation can be made, since this is equally soluble in the stronger acids. In fact, a soluble salt of any metal which has an insoluble hydroxide or carbonate can be transposed to another soluble salt of the same metal by precipitation of one of these and dissolving it in the acid
.
acid unites so strongly with the OH~ of the base, giving a " solution containing Cu 4 4", with H+ and Cl~ in excess. If, now, + and Cl" the excess of off this solution is
corresponding to the desired

53.
salt.
,
Aluminum
,
chloride,
oxide, A1 2 O 3 by first 4 OH, and then heating, which hydroxide, e.g., NaOH, aids the decomposition of the hydroxide into the oxide and the volatile substance steam. The two processes are repre,
A1C1 3 can be changed to aluminum precipitating A1(OH) 3 using a soluble
NH
224
by the
equations,
Ch. XIII
sented
3OH- = A1(OH) 8
and
2
A1(OH) 3 = A1 2 O3
+ 3 H 2 O.
,
into 54. To change sodium acid carbonate, NaHCO 3 sodium carbonate, Na 2 CO3 two methods are available. The salt can be dissolved in water and treated with 1 equivalent ~ of NaOH, when the HCO 3 will be neutralized by the added
,
OH", as shown by the equation
HC03- + OH- = C0 3
The
+ H 0.
2
3 on evaporation. resulting solution yields solid Na 2 the acid carbonate is capable of another kind of Again,
CO
decomposition, represented by the equation,

2
NaHC0 3 = Na2 C0 + H 2 O +
3
CO,.
of the substances produced by this reaction are volatile, the reaction can be made to proceed so as to produce them by heating the mixture in an open vessel so that they
Since
two
can escape.
to NaOH, it is necessary to remove and supply OH~. Since both sodium compounds are soluble, the insolubility of some other substances must be invoked. We need a hydroxide of some metal which is more soluble than the corresponding carbonate. The best Dne for this purpose is Ca(OH) 2 which is itself scarcely
55.
To change Na2 CO 3
the
CO3
soluble, especially in a solution of
NaOH. The
insolubility
of CaCO 3 causes the following reaction to take place, whereas any excess of Ca(OH) 2 together with the CaCO 3 produced,
,
can be filtered
off:
Ca(OH) 2
chloric acid, as
+ CO
= CaCO 3
+ 2 OH~
dilute
56. Iron rust can be dissolved
by moderately shown by the equation:

3
hydro
Fe2
H+ =
2 Fe+++
+ 3 H O.
2
In dissolving a rust or ink stain off a delicate fabric
it is
not
57
TYPES OF EQUILIBRIA
225
desirable, however, to use such concentrated acid. More + can be used if the reaction is aided dilute by the removal
one of the products. This is accomplished by using oxalic acid, which furnishes both dilute H+, since it is a rather weak which unites with the acid, and also oxalate ion, C 2 O 4 free ferric ion to form a complex ion (cf. paragraph 21).
of
,
The
reaction
is
Fe2 O 3
+ 6H C
2
Fe(C 2 O 4 ) 3
+3H
6 H+.
often highly desirable to keep the hydrogen ion concentration of a solution as nearly constant as possible,
57. Buffers. It
is
as
9
m
when measuring the

growth of
velocity of a reaction or
^^/ "^"^^ _-^-^pH
studying the
bacteria or plants, each species of which thrives
only
cu
07
o.9 i!o
through
certain
range. This can be accomo!i
0.2
Fraction of
HPO 4
~~
o'.3
in
0.5
o'.6
o'.8
a 0.1 molal mixture of and ['
HPO 4
plished by usingan approximately equal mixture of

ts
Fig. 1.
Phosphate
buffer.
j
mixtures of NaH 2 PO 4 and Na 2 HPO 4 The ionization con" HPO 4 is 6 X 10~8 stant of the reaction, H 2 PO 4 = H+ 8 i.e. (H+)(HPO 4 ) = 6 X 10- (H 2 PO 4 ") L If we mix the two salts to give a series of ratios (HP0 4 ) to (H 2 PO 4~) whose sum is 0.1 molal and calculate the corresponding values of (H+), we get the curve shown in Fig. 1 where
.
j^. ug consider
log (H+) or in a solution in

is
pH
is
plotted against the value of
which
(HPO 4~)
is
(H 2 PO 4~)
flat
(HPO 4 ") = 0.1. It
evident that the curve
rather
in
the region of
and HPO 4~, hence the an equimolal mixture of HPO 4 addition of a moderate amount of H+ or OH" to such a solution would cause but little change in pH; the mixture of the two phosphate ions thus serves as a "buffer" against changes in the acidity of the solution, and a process such as bacterial culture could be carried out in such a solution under
226
The above mixture could
8.0.
Ch. Xlll
controlled conditions.
evidently
be used for values of pH between about 6.5 and mixtures can be selected for other ranges. 1
Other
58. Hydrolysis: Quantitative Calculations. Since hydrolysis rep+ between the OH" of water and the resents competition for anion of a weak acid, such as C 2 3 O 2~, as explained in paragraphs
obvious that the concentration of the products of hydrolysis can be calculated from the dissociation constants of water and of the particular weak acid or base formed. Using the ~ ~" = HC 2 H 3O 2 hydrolysis of C2H 3 O 2 as an example, C 2 H 3 O 2 + H 2 O formed 2 H 3O 2 OH", we note first, that every molecule of results in the liberation of one of OH~, therefore their concentrations are identical, so we write, (HC 2 H 3 O 2 ) = (OH~). We choose
it is
23 and 24,
HC
the concentration of
since
NaC H O
2 3
in
the solution, say 0.1 molal, and

is
we know
3 2
that the
amount hydrolyzed
very
slight,
we can
(3)
set (C 2
H O ~) = 0.1. We have, = (OH! (1) (HC H

2
3
accordingly, four equations:
2)
(H+XOH-) = 10-"
which are simultaneous, and can be solved by the ordinary methods
- 10~ 5
.
of algebra. Substituting (1)
and
(2) in (4) gives
Writing
-
(H+)
(H+MO- 1 = (OH
)
1.8
2
10- 14 /(OH~),
from
.
(3)
gives
(OH~)
X =
10~ 15
1.8
10
10-*
1.8
X X
10~ 16 10~5
5.6
10~ u
To
take the square root of H
an exponential, we want an even exponent, therefore we write (OH"") 2 = 56 X 10~12 whence (OH~) = 7.5 X 10~ 6 Since, furthermore, ~ (HC 2 H 3O 2 ) = (OH~), we see that so little C 2 H 3O 2 was hydrolyzed that we were quite justified in setting its concentration at equilibrium
,
.
equal to the amount per liter put into the solution. In titrating acetic acid with alkali, we wish an end-point not
the solution
is
when
the acid and base are present in 6 equivalent amounts, when (OH~) = 7.5 X 10" and (H+) = 1.3 10~ 9 or pH ~ 9 (cf. paragraph 25). Thymol blue or phenolphthalein
neutral but
when
would serve the purpose. Hydrocyanic acid, HCN,

1
is
much weaker than
acetic, its ioniza-
Latimer and Hildebrand, Reference Book

III.
of Inorganic Chemistry,
Ap-
pendix
58
tion constant
is
TYPES OF EQUILIBRIA
4
227
2) therefore
10~ 10
(cf.
Chapter XII, Table
the
degree of hydrolysis of
CN~,
2
CN- + H
HCN + OH-
must be much greater than that of CoHsOj". Let us choose 0.5 Af-KCN, assume that (CN~) = 0.5, and see whether this must be corrected. Setting up the four equations as in the previous case,
(HCN) = (OH")
(CN*")
0.5
14 (H+)(OH~) = 10~ = 4 X 10~ 10 (HCN) (H+)(CN~)

14 = 4 X 10- 10 (OH~) 2 then Solving for (OH") gives, first, 10~ X 0.5 2 = and (OH") = 3.5 X 10~ 3 1.25 X 10- 5 = 12.5 X 10~6 (OH") But (HCN) = 3.5 X 10~3 also, and the true (CN") has not been
, .
reduced below 0.5 sufficiently to require any correction. In a case where the degree of hydrolysis is large, one must either use the method of successive approximation (cf, Chapter XII, paragraph 27) or else write, for a weak acid, HX, and its ion, X", (HX) (X") = concentration of salt taken, M, and (H+)[AT - (HX)] = (HX)K a
or (H+)[Af (OH") = (On~)*K a /K w (OH~)] = (OH")K a To solve this quadratic equation requires the troublesome operation
.
orM -
of completing the square. The hydrolysis of the ion of a
weak
If
base, of course,
is
dealt with
its ion,
by
is
essentially the
,
same method.
the
weak base
is
M + and ionization constant, Kb, the equation for the hydrolysis M + H O = MOH + H+ and the four equations are,
its
4
2
MOH,
(MOH) = (M+) =
(H+)
molality of
hydrolysis 10- 14
-K 6 (MOH)
salt,
is
unless
large.
very
+ (H )(OH") =
==
228
Exercises
Ch. XIII
See Appendix
1.
II for
Answers
will give
of the following substances, when added to water, an acid reaction, which alkaline, and which neutral: (a) NaCl, (6) CO 2 (c) NaAc,* (d) NaNO 3 (e) CaO, (/) K 2CO 3 (g) (NH 4)2SO 4 (A) Ca, (*) sodium borate, (j) BaCl 2 ?
Which
2.
Can you
Write
1
give a
way
for
demonstrating the hydrolysis of
A1 2 (SO 4)3 without an indicator?

3.
in order of decreasing acidities: 1

1
M-H 2SO 4
1
1
1
MJlf-
HAc,
M-NH^c,
Af-NaAc,
M-NH OH,
4
Af-HCl,
NH
4C1,
0.1 Jlf-Ba(OH)i.
4.
Arrange the following solutions
in order of decreasing con,
centration of
OH~: (a) 0.5 Jlf-NaAc, (b) 0.1 Af-Na 2 CO 3 (c) 0.1 Af-NH 4Cl, (d) 0.1 M-NH4Ac, (e) 0.1 M-NaOH, (/) 0.1 M-Ba(OH) 2 (g) a solution made by dissolving 0.112 g. of CaO in 200 cc. of water. 5. Why may it be necessary to use different indicators for
,
titrating different acids

6.
and bases?
indicator could you use to distinguish between (a) distilled water and 0.001 M-NaOH; (fe) 0.001 M-NaOH and 0.1
What
Jlf-NaOH? State the distinguishing colors in each case. 7. Which of the two salts, NaH 2 PO 4 and Na 2HPO 4 would be more hydrolyzed when dissolved in water? 8. What is the effect on a water glass (sodium silicate) solution
,
of
of (a) exposure to the ammonium chloride?

9.
CO 2
in the air; (b) the addition of
a solution
(a)
How
can you determine by experiment which of the
following reactions goes farther in pure water:
HCO
(b)
"
3
HCO +H
~
3
= H+ + CO ~~; = H 2 C0 3 + OPT?
3
What
10.
is
the net result of both reactions?
Point out the relation between the strengths of bases and acids and the hydrolysis of the corresponding ions.
How would you prepare (a) pure solid CuSO 4 from CuCl 2 pure solid CuCl 2 from CuSO 4 (c) CaCO 3 from CaSO 4 (d) CaSO 4 from CaCO 3 (e) solid NaCl from 4 C1?
11.
(b)
,
NH
12.
How
is
is
or
CaSO 4
*
could you determine by experiment whether more soluble in water?
CaCO 8
Ac
a convenient abbreviation for the acetate ion, C2HaO2~".
TYPES OF EQUILIBRIA
13. Describe a simple experiment that would enable you decide whether CaC 2O 4 is more or less soluble than CaCOs.
28<
tc
14. What substances would remain as solids and would be evolved as gases when solutions of the following are evaporated (a) Zn++, CF and excess of H+ and SO 4"; (ft) Zn++, CF and excess
of
H+
15.
and
(a)
NO
3?
Explain briefly
why
solid
BaCO and
3
solid
is
BaAc2
(ft)
are
soluble in dilute
HC1
solution while solid
BaSO 4
not.
Write
equations.
16.
(c)
2
What
3
is
H CO
solution,
the effect of (a) 4 C1 solution, (ft) 3 solution, upon a precipitate of Ca(OH) 2 ? Explain in
NH
HNO
each case.
17. If, when 2 moles of NaCl and 1 mole of 2 SO4 are brought together, the reaction ceases when the HC1 gas produced exerts a pressure of 10 atmospheres at 77 C. in a volume of 2 liters, (a)
how many moles each of NaCl and fraction of each has reacted (c) how
;
H SO
4 have reacted; (ft) what 2 might the quantities reacting
be increased?
18. Write the formulas of the various molecules or ions present and state the approximate concentration of each when the following are put into 1 liter of water: (a) 0.02 mole of CaCU, (ft) 0.02 mole of CaCl 2 and 0.03 mole of NaCl, (c) 0.02 mole CaCl 2 and 0.05 mole Na 2 C0 3 (d) 0.01 mole of CuCl 2 (e) 0.02 mole CaCl 2 0.02 mole Na 2 SO 4 and 0.02 mole Na 2 CO 3 (/) 1 mole NH 3 (g) 1 mole NH 3 and 0.5 mole NaOH, (h) 1 mole NH 3 and 1 mole HC1, (i) 1 mole NH 4OH, (j) 1 mole NH 3 0.1 mole AgNO 3 and 0.1 mole 0.01 mole AgNO 3 0.05 mole KC1, and 0.05 mole KI. NaCl, (*) 19. How could you determine experimentally whether the NH 3 the NH 4+ or the OH~ of an ammonium hydroxide solution is responsible for the formation of a complex ion with a nickel ion?
, ,
,
20. The following can exist together in equilibrium at suitable = 2 Ag(NH 3 ) 2+ 2 OH". concentrations: Ag 2 O 4 2O 3 how the equilibrium would be affected (a) by boiling, Explain
+H
+ NH
(ft)
(e)
by adding NaOH, by adding KNO 3

.
(c)
by adding
NH NO
4
3,
(d)
by adding Ag 2O,
be present and approximately at what concenthe following substances are mixed: (a) 0.1 mole 0.1 mole KOH, 1 liter of water; (ft) 0.1 mole ZnSO 4 22.4 3 liters of 3 gas at standard conditions, 1 liter of water; (c) 1 mole BaCl 2 1 mole CaCl 2 1 mole 2 SO 4 10 liters of water; (d) 1 mole Zn, 0.5 mole HgCl, 500 cc. of water?
21.
What would
when
,
tration
HgNO
,
NH
22.
How
would you prepare a pure
silver
compound and a pure
230
Ch. XIII
copper compound from a mixture of solid silver chloride and cupric hydroxide? Write equations.
23. In the following
Ac"",
list
o_f
ions:
H+, Ba++, Ag+,
NH
4+,
SO 4
CF,
CO
CN~, OH~,
combine largely
if
state each pair that would tend to brought together in dilute solution. In each case
give reason for your answer and write equation. 24. What is an amphoteric substance?
25. Can the following substances be present in moderate concentration in the same solution? If not, what is formed? H+ and
H+ and OH", H+ and SO 4 H+ and CO ", H+ and C 2O 4~~, CO ~", Ca++ and H 2 CO OH~ and H 2 CO H 2 CO and C0 ~~, HAc and CO "~, A1+++ and OH", Cu++ and NO ", Ag+
3 ~,
,
NO
Ca++ and
3
3,
3,
3 Hg++ and CF. Given the following reactions, arrange the compounds of copper involved so far as you can in a list according to increasing ++ ability to hold Cu (a) H 2 S gives no precipitate in a cyanide solution of copper; (b) copper sulfide is insoluble in ammonia; (c) ferrocyanide ion added to copper ammonia complex solution precipitates copper ferrocyanide; (d) copper hydroxide is soluble in ammonia.
and
NH
26.
27. Given the following reactions, arrange the compounds of lead involved so far as you can in a list according to increasing
ability to hold Pb++.
= PbS0 + 2 I", + S0 ~ + 3 OH"" = HPbO ~ + H O + PbCrO + 3 OH"" = HPbO + H O + PbCl + 21"== PbI + 2 OT, ~ HPbO + S + H O = PbS + 3 OH", PbI + CrOr"" = PbCrO + 2 F.
PbI 2 PbI 2
4
2
2
2 I",
CrO 4
*28. E>erive the expression for the concentration of solution of the salt, NaX, of molar concentration, M.
OH~
in a
a weak acid, with ionization constant, a of X" hydrolyzed is not sufficient to reduce tion appreciably below the amount taken, Af.
HX,
is
The acid, Assume that the

its
amount
*29.
concentra-
Use the formula derived

in 0.4
in the preceding exercise to calculate
(OH")
M-KCN. Take
.
for
HCN Ka =
lO" 10
*30. Calculate, as in Exercise 29, the (OH~) in_0.1 12 is is 10~ Note that enough 4 4 a for
M-Na PO
3
4.
HPO
indicate that
0.1
*
at equilibrium is' (PO 4 ) therefore the formula derived in Exercise 28

difficulty.
formed to appreciably less than

is
HPO
not sufficiently
TYPES OF EQUILIBRIA
231
accurate for so large a degree of hydrolysis. There are two procedures for obtaining a better value of (OH~). What are they? Use one of them to obtain (OH~) to within 10 per cent.
*31. Calculate the dissociation constant of
HC1O from
the value
(OH~)
10- 4 in 0.5
M-NaClO.
CHAPTER XIV
THE EFFECT OF PRESSURE AND TEMPERATURE UPON EQUILIBRIUM

in the last two chapters that it is possible, the concentration of one of the reactants in a by altering system at chemical equilibrium, to cause the equilibrium to shift in such a manner as would tend to restore the initial
1.
We have seen
concentrations, or, as
we may
say, to neutralize the
imposed
change. It is likewise possible to affect an equilibrium by changing the total pressure to which the system is subject,
temperature. We shall now inquire into the direction in which a reaction must proceed in order to restore equilibrium when subjected to such changes in presor
by changing
its
upon a System in Equilibrium. If we have an equilibrium between a liquid and its vapor, as discussed in Chapter III, we have seen that an
the
increase in pressure tends to cause vapor to condense, since number of molecules in the gaseous state is thereby
sure and temperature. 2. Effect of Changing Total Pressure
reduced, relieving the pressure. We have seen also that this is in harmony with the kinetic theory, and have stated, in Chapter XII, the general Theorem of Le Chatelier which
demands that any equilibrium system, no matter how complex, subjected to such an increase in pressure must likewise
tend to neutralize the change. Thus, an increase in pressure always tends to produce the system having the smallest
volume, a decrease
in
in applied pressure. If
volume tending to relieve the increase an applied pressure may be minimized
not only by the contraction of the substances composing the system but also by a reaction between them, the increase
CONTROL OF EQUILIBRIUM
233
in pressure will tend to cause that reaction to proceed which results in a diminution of the volume of the system. This
effect of pressure
on equilibria will, of course, be greatest in the case of reactions involving the largest change in volume, e.g., in reactions involving a change in the number of gaseous molecules.
3.
Suppose, for example, that

, ,
we have
a closed vessel
2 in equilibrium, which has been containing SO3 S0 2 and reached by the substances reacting in one direction or the O2 = 2 SO3 other, as represented by the equation, 2 SO 2
We
is
from the equation that when SO 3 is formed there a change in the number of molecules in the proportion
see
is
3 to 2. If pressure
it
applied to the three gases in equilibrium,
compress them, resulting in a decrease in volume. A further decrease is possible, however, by the union of some of the SO 2 with some of the O 2 the consequent diminution in the number of molecules relieving somewhat the pressure applied. Starting, in two experiments, with identical amounts
will
,
SO 2 and O 2 at the same temperature, we find that more SO 3 will be produced when equilibrium is finally attained
of
the pressure is high than if it is low. The same conclusion may be drawn with respect to the reaction for the synthesis of ammonia, whose equation is
if
N + 3 H = 2 NH
2
2
3,
which shows that ammonia
is
formed
with a dimution
in the
number
of molecules.
high pressure
would fayor that reaction which would yield the smaller

volume, thus relieving, as far as possible, the high pressure
applied. On the other hand, with the equilibria, 2 C1 2 = 2 HC1, with no change in the and 2
N +O =
H +
2 NO, 2 number of
gaseous molecules during reaction, pressure will be without effect on the amounts formed. 4. In predicting the effect of pressure we must have regard to the physical states of the substances involved under the conditions of the experiment. It is possible, for instance, by
2 S directly using either liquid sulfur or sulfur vapor to make from its elements. The respective reactions may be represented
234
Ch.
XIV
by the equations,
2
H +S H +S
2
(liquid)
(vapor)
= H 2 S, = 2 H 2 S.
no change
in
In the
if
first
reaction there
is
practically
volume,
the reaction is carried out at constant pressure, since the volume of the liquid sulfur is negligible. Therefore, the
present at equilibrium will be practically independent of the pressure applied, or of the volume of the vessel in which the reaction takes place. In the second process, where the conditions are such that the sulfur is in the vapor state, the formation of H 2 S at constant pressure results in a decrease in volume, hence the higher the pressure the greater the amount of H 2 S formed. 5. Not only is the effect on the direction indicated by the above discussion, but its magnitude also depends upon the magnitude of the volume change during the reaction. Thus a tenfold increase in total pressure will produce a much greater increase in the amount of 3 produced from 2 and H 2 than in the amount of SO 3 produced from SO 2 and O 2 since the decreases in volume in the two reactions are respectively from 4 to 2 and from 3 to 2. For the same reason, very great changes in pressure have to be applied in order to have much effect on equilibria involving liquids
relative of
amounts
H2
and
H 2S
NH
and
solids only,
where only small changes
in
volume occur.
6. The influence of pressure on a gas phase equilibrium may be calculated quantitatively by noting that the effect of the pressure is exerted solely upon the concentration of the reagents and not at
all
on the molecules themselves. Accordingly, the equilibrium constants derived in Chapter XII are independent of total pressure. In terms of kinetic theory, it is clear that any increase in pressure increases the concentration of all the reactants and hence speeds up
both the forward and back reactions in each equilibrium. Therefore the two reactions involve no change in the number of molecules, as in N2 C>2 = 2 NO, a change in the total pressure causes no 3 Hz = change in equilibrium concentrations; but if, as in N2
if
the reactions involve different numbers of molecules, the equilibrium will shift toward the side with the smaller number in
2
3,
NH
kinetic theory. This
is
235
harmony with the

expressed in
clear
expressions for the equilibrium constants for these
from the quantitative two reactions,
number
of moles in the volume, V.
Take, moles
110
2
2
N +
x
x x
1
1
NO
130
N +
2
H =
2
NH
Amount
Amount
reacting
x
1 1
x
x x
2
x
3
3
present at
equilibrium
1
1
x x
3 x 3 ~~ x
2 2
Equilibrium concentrations
2 x
y =
(1
V
2
V
(1
~V
Equilibrium constants
4x
x)
2
s)(3
2
3 x) 3
4# F
The volume has canceled out for the first reaction but not for the second, where the smaller we make V by increasing pressure the larger x must become to compensate. If, for example, for the latter = 0.1 when V = 1001., K = 0.0443, then, if presequilibrium x
sure
is
applied to increase x to 0.2, the corresponding volume would

1.
be 39.5
7.
Effect
is
on Equilibrium of Changing the Temperature.
What
the effect of changing temperature upon a system
at equilibrium? What, for example, will happen if a closed vessel containing SO2, O2, and SOa, which has been allowed to come to equilibrium at 500 C., is transferred to an oven in
which the temperature
is
550 C.? Let us write
down
the
equation for the reversible reaction, including energy in the equation just as though it were one of the reactants:
2
S0 2
SO 3
46 kcal.
Bringing the reacting mixture to a higher temperature, i.e., supplying heat to the system, can be regarded (somewhat " concentration of heat." The naively) as increasing the
up part some SOs will decompose into O 2 and S0 2 Thus, the principle of Le Chatelier leads to the useful rule:
system
will accordingly
i.e.,
change
in
such a
way
as to use
of this heat,
An
increase in temperature will bring about that shift of equilibrium which absorbs heat.
336
of
Ch.
XIV
The formation
example
:
NO
2
from
44
its
elements provides another
N +O +
2
kcal.
NO.
Since heat
is
absorbed, a high temperature will favor the
formation of NO. 8. Considerations of this sort apply to every sort of equilibrium and enable us either to predict the effect of changing the temperature from the sign (and magnitude) of the heat of reaction, or, conversely, to predict the latter from the former.
As an illustration, let us consider potassium chloride, which is much more soluble in hot water than in cold water. If potassium chloride be added to water, absorbed? From the solubility behavior,
reaction of dissolving potassium chloride
is
heat liberated or
that the
we conclude
must be
KC1
Therefore,
(solid)
heat
= K+
(aq)
Cl"
(aq).
heat
when potassium
9.
is absorbed (the chloride dissolves.
solution
becomes
cooler)
effect on equilibrium is, mainly, due to the between the force of chemical binding and the natural competition tendency of a molecule to fly apart if no force is holding it together. Kinetic theory tells us that as the temperature is increased, each molecule experiences an increasing number of violent collisions, many of which are energetic enough to break chemical bonds. As a result,
The temperature
at high temperatures the influence of chemical binding energy be-
comes of less importance, the reaction rather proceeding so as to give

the
maximum number of separate molecules. Conversely, at low temperatures the influence of binding energy dominates; and those molecules are formed preferentially whose chemical bonds are the
strongest.
10.
is
given
The quantitative dependence by the relation

4.571ogio#
of equilibrium
on temperature
= AS -
Here AJ7 and AS are quantities characteristic of the particular reacAH is the heat of the reaction, and AS is called the entropy change of the reaction. As the equation above suggests, a graph of
tion;
11
237
the logarithm of against the reciprocal of T gives a straight line. Fig. 1 gives such graphs for the SOa synthesis and the synthesis discussed in Paragraph 7.
NO
0.4
0.6
0.8
1.0
1.2
1000 /T
Fig.
L The
dependence of equilibrium constants on temperature.
11.
Reactions. In Chapter
cal reactions, as
it is
Simultaneous Consideration of All Factors Governing XI we considered the velocity of chemiaffected
by concentration, temperature,
and the presence
of catalysts. have also considered separately the effect of concentration, pressure, and temperature
We
upon chemical equilibrium and are now prepared to consider the simultaneous effect of these factors in controlling chemical reactions. We must again emphasize the fact that the question
of velocity
is quite distinct from that of equilibrium. If we should put some calcium fluoride, CaF2 and some calcium sulfide, CaS, into separate beakers of water, we might con,
clude from a hasty examination that both are very insoluble. As a matter of fact, the small amount of the solid going into
is due to very different reasons in the two cases. Calcium fluoride is truly insoluble, and no amount of time or stirring would cause more than a very small amount of it to dissolve. Calcium sulfide, on the other hand, is insoluble because, in order to dissolve, it must hydrolyze, giving Ca"f OH~, and SH~, a process which takes place very slowly. Again, calcium chromate, CaCrO4, is more soluble in cold water
solution
~,
238
if
Ch.
XIV
than in hot,
sufficient
time
will
is
become saturated, but
it
dissolve
allowed for the solution to much faster in hot
water than in cold, so that after a given time more might be found in a hot than in a cold solution, although eventually the latter would contain more of the salt. It is thus very
important, in attempting to realize difficult reactions, to remember that speed and equilibrium require independent considerations, and that conditions which favor the desired
equilibrium may not favor its rapid attainment, and vice versa. A discussion of the complete conditions for realizing certain important reactions will make this clearer.
We
The "Contact Process" for Making Sulfuric Acid. have seen above that to make SOs from SC>2 and O2 a low temperature is desirable in order to give the most complete
12.
yield
of SOa.
By
will
however,
we
recalling the discussion in Chapter see that the lower the temperature
XI,
the
more slowly will the desired equilibrium be reached. We must therefore distinguish between the amount of SOs which would be produced at equilibrium and the amount that would be produced in a given time. The time necessary for
reaching equilibrium grows enormously as the temperature is lowered, with the result that it is practically impossible
to reach equilibrium except at high temperatures, where the amount of SO 2 converted into SOs is so small that it would
not be profitable to use the reaction. In order to work at a temperature at which the equilibrium is favorable a new factor must be introduced to increase the velocity. This is accomplished in practice by passing the
gases over a solid catalyst of either finely divided platinum or some form of vanadic oxide, XÔs. (Hence the name
"contact process.")
be brought out by the curves in the accompanying figure (Fig. 2) where the solid line indicates the per cent of the total possible amount of SOs which would be obtained at various temperatures if sufficient time were allowed for equilibrium to be reached as a function of the temperature at equilibrium. The dotted lines in Fig. 2
effects
These
may
12
239
indicate the actual nearness of approach to equilibrium with
no catalyst present (curve

(curve 2) for the
same
1) and with a catalyst present rate of flow of the gases through the
2', show the corresponding nearness of approach to equilibrium if the rate of flow is increased in each case, i.e., the time allowed for reaction is less. These data are for a gas mixture at one
heated chamber.
The dashed
curves,
and
atmosphere total pressure containing 79% N 2 by volume.
7%
S02,
14%
O2,
and
200
400
600
800
1000
1200
1400
Temperature
curves
1
Approach to equilibrium in the conversion of SO? and C>2 into S03 without catalyst curves 2, with catalyst at two different rates of flow, and 2 slower than 1' and 2'.
Fig. 2.
1,
; ;
In commercial practice
conversion but rather
flow gives
does not give a close approach to equilibrium at a favorable temperature and requires more expensive plant outlays. A balance must be struck at which the cost per ton of product is a minimum. The product, sulfuric acid, is obtained by dissolving the fog of SOs in concentrated sulfuric acid (it is not readily absorbed by water), and then diluting with water to give
the desired concentration.
maximum is produced may be too low for economy. A flow may give a higher rate of production but
not desired to get maximum optimum conversion. A low rate of conversion but the rate at which product
it is
rapid rate of
240
Ch.
XIV
13. The speed of the reaction, and also the desired equilibrium, might be influenced in the right direction by having the reaction take place under high pressure, but this would involve difficulties in the way of more complicated con-
and operation that are not required for adequate SO 2 must be paid for, while the 62 is obtained it is more important to use up the SO2 than the 62. This is done by taking the air in concompletely
struction
yields. Since the free from the air,
siderable
excess,
3-
required.
We may
equivalent amount summarize in tabular form our conclusions
or
4-fold,
of
the
concerning the best conditions for realizing this reaction.
14.
The Synthesis
2
of
Ammonia.
2
If
we compare
the reaction
for the synthesis of
ammonia,
2
N +3H =
NH
AH = -
24 kcal.
with the above reaction for making
SO.3,
we
see that the
same conditions are indicated
for realizing this reaction as
is exceedingly slow, so that even with iron, the best catalyst that has been discovered after extensive search, advantage must be taken
for the former. This reaction, however,
of high pressure in aiding both the speed and the equilibrium at the temperatures at which the reaction will take place
with measurable velocity. The effect of both temperature and pressure on the yield
of
NHs
at equilibrium
C.
is
indicated in the following figures:

At
Yield of 1 atmospheres
NH
in per cent
Temperature,
At 100 atmospheres
1,1
800 700 600 500
0.011 0.021 0.048

0.13
2.1
4.5
10.8
15
241
A further lowering of temperature below 500 C. to improve the yield would give too slow a reaction, so that the process is worked at about this temperature, and under pressures
up to 1000 atmospheres. As the N2 and H2 pass over the catalyst they unite partially to form NHs. The gases are then passed through a cooling coil in which the NHs is condensed to liquid and removed, or the NH 3 may be re-
moved by bubbling the gas mixture through water to give aqua ammonia. The N2 and H 2 again pass over the heated catalyst, again forming the equilibrium amount of NH 3 and so on. The removal of NH 3 is compensated for by pumping in fresh HU and N2. It is of interest to note that this process enabled Germany to prolong the First World War by several years after being
,
cut off from the natural sources of fixed nitrogen" from Chile saltpeter, Both fertilizer and explosives NaNOa.
require
"
combined nitrogen in their preparation and this process gives an inexhaustible supply from the nitrogen in the air and the hydrogen in water. Before 1913 no nitrogen
was
all
fixed in this manner, while in 1940 over 50 per cent of manufactured nitrogen compounds stemmed from synthetic ammonia. 15. The Synthesis of Nitric Oxide. We have already referred
briefly to the reaction,
N +O =
2 2
NO,
we
AH = +
44 kcal.
We
see that the formation of
NO
would be aided by the
following conditions, which
will tabulate as before.
Pressure, Temperature,
and Equilibrium
To favor high speed
either of formation
To favor large amount of NO

at equilibrium
or decomposition
Total pressure
No
effect
Temperature
High
High High
Aa a consequence
of these conclusions,
we
see that
NO
should
be formed more rapidly and also more completely at high
242
Ch.
XIV
temperatures. That this is true is seen from the following figures on the basis of experiments:
Temperature, C. Per cent NO at equilibrium, starting with air
1540
0.37
1920
0.97
2930
5.0
3930
10
Obviously NO is stable, in a true sense, only at extremely high temperatures, and both a favorable equilibrium and high speed in attaining it are aided by high temperatures such as those given by an electric arc. The problem is then to lower it to ordinary temperature without letting the equilibrium shift back to N 2 and O 2 as it cools. This is done by cooling it sufficiently rapidly as the gas mixture leaves the arc. There is also an electrical effect, due to the arc, tending to give a greater yield than is indicated by the above
conditions of ordinary equilibrium.
NO unites readily with more which will dissolve in water forming a mixture of nitric and nitrous acids. The N 2 O* may also be passed over slaked lime, giving a mixture of calcium nitrite and nitrate, which is used as fertilizer to supply nitrogen to the soil. This process was once used successfully on a commercial scale in Norway, but is now of only academic
At ordinary temperatures
O2 to form
N O4,
2
interest.
"Synthetic" Gasoline. Octane, C 8 18 one of the typical hydrocarbons obtained by distilling petroleum, is a principal constituent of gasoline. However, the distillation of petroleum yields a variety of hydrocarbons, including many of higher
16.
,
molecular weight than octane, which are not volatile enough

for gasoline, and of lower molecular weight, which are too volatile for gasoline. In the development of processes for
converting these heavy and light hydrocarbons into gasoline, the principles set forth in this chapter have been of great aid,
by
ditions.
indicating which reactions will be favored by certain conBy way of illustration, let us examine a few of the
reactions
by which octane might be
synthesized.
An
8-carbon molecule can be produced by splitting a 16-
16
:
243
carbon molecule into halves, or by the union of two 4-carbon

molecules
C 4 Hio
The
first
C 16 H 34 = CgHig + C 4 H 8 = C 8H 18
+CH
8
16
AH = + AH = is
19.1 kcal. 13.5 kcal.

it
reaction, called ''cracking/'
endothermic so
is
at a temperature of 500 C. The second reaction, called "alkylation," is exothermic and must be brought about at low temperatures,
catalyst,
favored by high temperatures. makes use of an alumina-silica
typical
cracking process
Alkylation is in practice carried out at room temperature or below, with HF or 2 S0 4 as a catalyst. The molecule C 8 Hi 6 produced in the cracking reaction, requires one more molecule of hydrogen to convert it to
H
,
octane
C 8 H 16
temperature
+ H = C 8H
2
18
AH = -
31.1 kcal.
Since this hydrogenation
is
exothermic,
it is
favored
by low
(for example, room temperature, with a platinum or nickel catalyst). At a higher temperature, the reverse reaction, dehydrogenation, occurs readily. Toluene, CeHsCHs,
and butadiene,
C 4 H6,
C 4 Hio
respectively,
can be manufactured from C 7 Hi 6 and by dehydrogenation at about 500 C.
over a chromia catalyst.

It is possible to
carbons)
8
by
prepare octane (along with other hydrothe hydrogenation of coal, or of carbon monoxide;
2
AH = + 9 H = C Hi = C Hi + 8 H O AH = 8 CO + 17 H
C
8
8
2
52.8 kcal.
306.6 kcal.
Both of these reactions are exothermic, so are reversed at excessively high operating temperatures. For the former, a
high pressure of hydrogen (200 atm.)
is
desirable.
The
latter
("Fischer-Tropsch synthesis") proceeds satisfactorily at ordinary pressures, about 200 C., over a cobalt or iron catalyst.
Exercises
1.
If
the volume of a solution

it
is is
water from which
change when pressure
greater than that of the salt and will the solubility of the salt applied to the saturated solution?
is
made, how
244
2.
Ch.
XIV
displaced
In which direction would each of the following equilibria be by decreasing the total pressure? (Explain.)
NO =
2
NO
2
2,
HC1 =
H +
2
C1 2
C
3.
(solid)
S 2 (vapor)
= CS
(vapor).
of heat.
4.
Ammonium How is its

The
chloride dissolves with considerable absorption solubility affected by the temperature?
solubility of
sodium chloride increases very

concerning
its
temperature.
What can be concluded
slightly with heat of solution?
5. When AgCl is prepared by mixing its ions heat is evolved. Is the precipitate more soluble in hot or in cold water? (Explain.) 6. Explain how temperature would affect the production of S = H 2S heat. according to the reaction: H 2
HS
2
benzene from acetylene according to the 137,700 cal. takes place slowly at a high temperature (benzene being a vapor) and is reversible. (a) What weight of benzene could be made by the complete conversion of 49.3 liters of acetylene, measured at 27 C. and 1
7.
The formation
2
of
6
reaction 3
CH = C H
2 6
atmosphere?
(b) State and explain the experimental conditions you would adopt to secure the maximum yield of benzene from acetylene in a
given time.
neutralization of strong acids by strong possible to decide how the ionization of water varies with the temperature. Trace the connection.
8.
bases evolves
Knowing that the much heat,

is
it is
9.
Acetic acid
more highly ionized at higher than at lower

of the following reactions, consequently, will
temperatures. Which evolve more heat?
+ OH- = H O; HAc + OH- = H O +

H+
2
2
Ac-.
is
10. Equilibrium at 1000 C. and phase of the reaction
atm.
reached when the gas
CO
(gas)
+C
(solid)
CO
(gas)
95,000 cals.
consists of about 99 per cent CO. What changes in conditions 2? you make to obtain a gas phase consisting chiefly of
might
CO
equilibria following reactions:
(a)
(6)
(c)
J45
11.
Comparing
between the substances involved in the
(d)
- 2800 cals. (gas) = 2 CO - 95,000 cals. CaCO = CaO + CO - 23,200 cals. 2 SO + O = 2 SO (gas) + 44,000 cals.
H +
2 2
2
I2
(gas)
HI
CO + C
3 2
(charcoal)
2
() 3
H +N =
2
NH +
3
24,000 cals.
(1) for
Designate by letter the equilibrium
which an increase in
total pressure, with temperature kept constant, would cause (a) the least effect, (6) the greatest shift to the right; (2) for which an
increase in
temperature, at constant volume, would cause the
greatest shift (a) to the right, (&) to the left.

*12.
produced.
the
2
When H 2 is burned against ice, small amounts of H C>2 are Two explanations for this have been offered: one, that
2
H
2 2
2
2
is
HO
produced by shifting the equilibrium, 2 H 2O + O 2 = heat, towards H 2O 2 at high temperatures; the other, that
two reactions occur,

2
H +O = HO
2
2
2,
followed
by
HO =
2
the latter being incomplete due to the rapid cooling of the flame. Can you suggest any experimental study that might serve to decide between these explanations?
2,
HO+O
Question of greater
difficulty.
CHAPTER XV
OXIDATION AND REDUCTION

In the previous chapters our attention has been largely confined to reactions in which there are no changes in oxida1.
tion
made
number. In Chapter IX, however, brief mention was of reactions in which such changes do occur, and it
was there pointed out that oxidation consists essentially of an increase in oxidation number, or loss of electrons, and reduction of a decrease in oxidation number or gain of electo give fuller attention to such the writing of equations representing them, and, second, the oxidizing and reducing powers of the substances involved. 2. Whenever an element is oxidized some element must
trons.
We
are
now prepared
first,
reactions, considering,
oxidized
be reduced. The substance containing the element which is is called the reducing agent, since it is responsible for the reduction of the other element. Conversely, the substance which causes an increase in oxidation number is the oxidizing agent, and contains an element which is reduced,
The
following table illustrates these terms:
Cu
Oxid.No.
+2H
SO 4 = CuSO 4
6
2,6
+ SO2 + 2 H 2O.
4
Element oxidized, Cu. Element reduced, S.
Oxidizing agent,
H 2 SO 4
Reducing agent, Cu.
H2 S +
Oxid. No.
I2
= S
H+
r.
1
2
S.
I.
Element oxidized, Element reduced,
Oxidizing agent,
I2 .
Reducing agent,
946
H 2 S.

2 Fe+++
+H
SO3
+HO
2
= 2 Fe++ + SO " + 4
247
Oxid.No.3
26
+5
Element oxidized, S. Element reduced, Fe.
Oxidizing agent,
Reducing agent,
H 2 SO3
MnO 4~ + 5
Oxid.No.
72
Fe++
+ 8 H+ =
Mn++
23
Fe+++
+ 4 H2O.
~".
Element oxidized, Fe. Element reduced, Mn.

3.
Oxidizing agent,
MnO 4
Reducing agent, Fe++.
Writing Equations for Reactions Involving Oxidation
and Reduction. The Substance Produced. Before an equation can be written for any reaction it is necessary to know what substances are produced. This may be determined by experiment or predicted, in most cases, from a knowledge of the reacting substances. For example, when hot concentrated
sulfuric acid reacts with
copper
it is
possible to detect the
evolution of sulfur dioxide by its odor, and the production of copper sulfate by the blue color it gives on the addition
of water.
When
sulfurous acid acts upon ferric ion, the ferrous
ion produced shows its presence by its faint green color, or by other characteristic tests, and the formation of sulfate
ion can be proved by adding barium ion. One sufficiently familiar with the chemistry of iron and of sulfur would not
need these
in
tests, for
oxidation
ferrous ion,
he knows that when ferric ion decreases number in acid solution it usually becomes and that the corresponding increase of oxidation
of sulfurous acid
numbers on the part

It is therefore
would give
sulfate ion.
important to know the oxidation numbers
the elements are capable of assuming and the compounds characteristic of each oxidation number. 4. For example, many of the metals, including the alkali
and alkaline earth metals, silver, zinc, cadmium, and aluminum, exhibit only one oxidation state in addition to that of the free metal, which is zero. Therefore a substance like aluminum ion, A1+++, cannot be oxidized farther, nor can
248
Ch.
XV
it be reduced to metal in water solution. Hence we would not expect it to take part in any oxidation or reduction process in aqueous solution. Chlorine shows the following
oxidation states, 7, which cor1, 0, +1, +3, +5, the compounds tabulated in Chapter X, pararespond to graph 9. Consequently, we would never find the chlorine in
CP, acting as an oxidizing agent, because it is as completely reduced as it is capable of being. already Likewise, if chlorine, C1 2 acts as an oxidizing agent it must be reduced, and the only probable product would be chloride
chloride ion,
,
ion or one of
its
compounds. Again, knowing that chlorine

Cl"
reacts with hydroxide ion as follows:
Cl a
+ 2 OH- =
CIO"
HA
in alkaline
,
we know that when CIO" acts as an oxidizing agent
solution, the chlorine could not be reduced to the next lower oxidation number, zero, corresponding to C1 2 but would
be reduced
5.
all
the
way
to chloride ion.
The
teristic of
following table represents the substances characchromium in the oxidation numbers of three and
six respectively,
and
in acid, neutral, or alkaline solution:

Acid
Neutral
Oxidation number
Alkaline
Cr+++ Cr 2 O 7
Cr(OH) 3
CrO 4
CrO2 CrO 4
~"
In accordance with the knowledge thus summarized, we would expect Cr*"^ to be produced when a reducing agent Similar information should be remem,acts upon Cr2 7
.
bered
in
for
the other
common
elements giving compounds
which they show more than one oxidation number. 6. The Assignment of Oxidation Numbers to the Elements Oxidized and Reduced. Having decided upon the substances produced by the reaction, the first step is to write their
formulas, together with those of the substances reacting, upon the appropriate side of the equation, and to assign an oxidation number to the elements oxidized and reduced,
as explained in Chapter V.

7.
249
Let us
illustrate the process
for the oxidation of Fe ++
by
MnO 4
by balancing the equation ~~. The following scheme
thus gives the various steps involved:

(a) Substances in
which oxidation numbers change
(b)
(c)
Oxidation numbers
(d)
(e)
Changes per atom Atoms required

Molecules required
5
+1
27
5
1
Fe++
" + Mn0 4 =
(f)
Other molecules added to balance

5 Fe++
~ + MnO 4 + 8 H+ =
5 Fe+++
Mn++
+4HO
2
Step (c), the change in oxidation number per atom, is found by noting that the iron changes from 2 to 3, while the manganese changes downward, from 7 to 2. To balance the reduction of 1 atom of manganese thus requires 5 atoms of
iron, as
shown
in step (e).
The
oxidation and reduction are
now
coefficients assigned disturbed in the final balancing of the other
balanced, and the
must not be elements and
may consider, first, either the disatoms, or the discrepancy in charges. crepancy oxygen It will usually be found somewhat simpler to begin with the 10 latter. In step (e) we have on the left 1 or 9,
charges.
this
in
To do
one
and on the right +15 + 2 or +17. We must, therefore, either add 8 H+ on the left or 8 OH~ on the right. Since the
metallic ions given in the equation could not exist as such in an alkaline solution the solution is acidic, and we should
add 8 H+ on the left. It will then be found that these 8 hydro~ gen atoms and the 4 oxygen atoms of the MnO 4 will be balanced by adding finally 4 H 2 O on the right, giving step
as the completed equation. Let us next consider a reaction occurring in alkaline will indicate the steps used in balancing it just solution.
(/)
8,
We
as in the preceding example.
250
which oxidation numbers change
-
Ch.
XV
(a) Substances in
CrO2
(b)
(c)
CIO"
1
= CrO4
6
" + CP.
1
Oxidation numbers
(d)
(e)

Molecules required
2
3 3
2
CrO2
CIO" =
CrO 4
~ + 3 CP.
(/)
OH" on left, and to balance oxygen and hydrogen, H 2 O on right, getting CKV + 3 CIO" + 2 OH" = 2 CrO 4 + 3 OT + H 2 O.
To
balance charges, add 2
9. There is sometimes confusion due to the presence in the same molecule of more than 1 atom of an element oxidized or reduced. As an example we will consider the oxidation of
SO 2
we
to
SO 4
exists only
(in acid solution, since Cr 2 7 by Cr2 7 in acid solution). Using the same steps as before,
have,
(a)
Substances in which oxidation numbers change
SO 2
(6)
Cr2 Of~
Cr+++
S0 4
~
".
Oxidation numbers
(of 1
atom)
46
2
36
2
(c)
(d)
(e)

Molecules required
3
SO2
Cr2 O 7
"=
Ci+++
left,
SO 4".
(/)
To
3
balance charges add 2
H+ on
and to balance
S0 2
H and O add H 2 O on right, getting " ~ + Cr2O + 2 H+ = 2 Cr+++ + 3 SO 4 + H2 O.

7
,
*
point to notice is that the required 2 atoms of Cr are whereas the coalready taken in the molecule of Cr2 O 7 " on the right. efficient 2 is required before the Cr^ 10. We will take next a reaction in which the same element
The
is
both oxidized and reduced,
viz.,
the reaction of active
12

,
251
phosphorus with concentrated NaOH solution to form phosphine, PH 3 and hypophosphite ion, H 2 PO2~~.
(a)
Substance in which oxidation number changes
P4 =
(&)
(c)
Oxidation numbers
Changes per atom
(d)
(e)
Atoms
required
(/)
Molecules required To balance charges add 3
P4 =
431
1
H 2 P02- + PH3 3 +1
3
H PO ~ + PH
2 2
3.
OH"
2
on
left,
and to balance
H
11.
and
H 2 O on left, getting = 3 H 2 PO 2 ~ + PH P 4 + 3 OH" + 3 H

add
3
3.
some, and we
(a)
Equations involving peroxides are sometimes troublewill therefore include one illustration. Substances in which oxidation numbers change
H O2 + MnO 4 ~ =
2
(6)
(c)
Oxidation numbers Changes per atom
17
5
1
Mn++
2
+O
2.
(d)
(e)
Atoms
required
Molecules required
5
~ + 2 MnO 4 =
Mn++
+5O
2.
(/)
6
12.
To balance charges, add 6 H+ on left, etc., getting ~ H+ + 5 H 2 O 2 + 2 MnO 4 = 2 Mn++ + 5 O 2 + 8 H 2 O.
An
it
Alternative Method. Since an element
is
oxidized
gives up electrons and reduced when it takes on electrons, the number of electrons transferred may be made
when
the basis for balancing an equation. For example, whenever ~ is reduced in acid solution it becomes Mn++. To 4 ~ there will take care of the oxygen atoms in the 4
MnO
MnO
obviously be required 8 H+, giving 4 2 O and to balance the charges will require 5 electrons, giving for the oxidizing half of the reaction the half-equation,
MnO 4 + 8 H+ +
The same
result
is
~~
5 e"
r
= Mn++
+ 4 H O.
2
achieved by writing in
first
the 5 electrons
252
Ch.
XV
necessary to change the manganese from oxidation number 7 to oxidation number 2, and then adding the 8 H+ to produce 4 2 O. If the substance oxidized is Fe++, the reducing half
is Fe++ = Fe+++ + e~. Obviously the former can take the electrons from 5 times the latter, so process that multiplying the latter half-equation by 5 and adding to the former gives
of the reaction
Mn0 4 +
"
5 Fe++
H+ = Mn++
5 Fe+++
+ 4 H2 O,
the same result as was previously obtained by the other
method. 13. Let us give an

in
alkaline solution
illustration of the balancing of a reaction " by this method. To oxidize CrO2 to
CrO 4
requires 4 OH"", giving ~
CrO 2
+ 4 OH~ =
CrO 4
+2HO+
2
3 <T,
the 3 electrons being obviously necessary to

balance.
make the equation

OH",
so that
To
reduce C10~ to Cl~ requires
2 0,
giving 2
CIO"
+HO+
2
2 e~
= Cr
OH-.
Multiplying this half-reaction by 3 and the former by 2 and adding cancels out the electrons, giving
2
CrO2
CIO-
+ 2 OH~ =
CP +
CrO 4
+ H2 O.
Although these methods may appear to be superficially different they rest upon the same theoretical foundation and will give identical results. It should be evident that gain in
14.
number is arithmetically equivalent to loss of so that there is no essential difference between electrons, the two methods where complete equations are involved.
oxidation
When
in electric cells,
dealing with the half-reactions occurring at electrodes, it is, of course, important to have the electrons
appear in the equations. Thinking in terms of electrons avoids the necessity of assigning oxidation numbers in cases where their location in a complex molecule or ion is not clearly evident, as in the case of S2 O 3 (cf. Chapter IX, paragraph 7) where 8 electrons
,
15

when S2 O3
is
253
SO 4~~. It should be understood, however, that oxidation numbers do not need to be theoretically correct in order to permit the correct balancing of equations, they need only to be arithmetically
are given of?
oxidized to 2
consistent.
Relative Oxidizing and Reducing Powers of Various Substances. The Metals and Their Ions. It was that a metal having a smaller pointed out in Chapter
IS.
The
affinity for its electrons can give them up to an ion whose affinity for electrons is greater. This is illustrated by the following reactions, all of which take place quite readily:
+ Zn++ Zn + Fe++ Fe + Pb++ Pb + Cu++ Cu + Hg ++ Hg + Ag+

Na
2
= = = = = =
+ 2 Na+, + Zn++, Pb + Fe++, Cu + Pb++, 2 Hg + Cu++ Ag + J Hg ++.

Zn
Fe
2
In each of these cases the baser metal
is
oxidized
by the
ion of the nobler one, and it is evident that zinc will reduce not only ferrous ion, but lead, copper, and silver ions as well.
Likewise, silver ion can act as an oxidizing agent, not only to copper, but to all of the other metals represented. In all
cases the metals act as the reducing agents, their reducing power decreasing as we descend the list, while the ions act
as oxidizing agents, their oxidizing power increasing as
we
1.
descend the
list.
This behavior may be summarized in Table

TABLE
1
g ^
Weak Na+ Na
Strong
Oxidizing Agents
Zn++ Zn
Fe++ Fe
Pb++ Cu++ Pb Cu
Hg2++ Hg Ag
Weak
^
Strong
Reducing Agents
This table has been arranged so that any ion will be reduced brought in contact with a metal to the left in the table. In order, however, for this arrangement to hold, the ions must all be in approximately equal concentration. If this
if
*54
is
Ch.
XV
Hg2
not the case, the positions of some + have about the same 4" and
f
"
may
Ag
be reversed. Thus oxidizing power, hence
the reaction,
}
is
Hg2++ + Ag = Ag+ +
by changing the
Hg,
easily reversible
relative concentrations.
"
principles of equilibrium set forth in Chapter XII apply " here also, so that a high concentration of Hg2 H and a low concentration of Ag+ favor the reaction as read from left to
The
right, whereas the reverse reaction is favored by reversing the relative concentrations. With most pairs of metals the
corresponding reversal requires greater differences in concentration.
Many interesting applications of oxidation-reduction series are possible. For example, it is evident that if a piece of zinc is put into a solution of ferrous ion there is a tendency for the latter to be reduced.
16.
Galvanized Iron.
this
Accordingly, if zinc and iron are in contact in an oxidizing solution, the former will be dissolved before the latter. This is the reason for the protective action of the zinc coating
on "galvanized"
iron.
When a piece of zinc is dropped into a solution of one of the ions to the right of it in the table, a reaction takes place such as the following
17. Electric Batteries.
:
Zn
Cu++ = Cu
Zn-H-.
Now this may
be regarded as a transfer of positive electricity from the copper ion to the zinc, or, better, as the transfer of negative electrons from the zinc to the copper ion. If this transfer of electricity can be made to take place through a wire we will have an electric current, and the reaction can be made to do work. To do this the zinc must not be put directly into the solution of copper ion, but electrodes of the two metals must dip into solutions of their own ions, the solutions being separated by a porous partition or by the
aid of their difference in density, as in the case in the "gravity
18

At the
:
255
cell," illustrated in Fig. 1.
zinc electrode the following
process tends to take place
Zn = Zn++
2 e~,
is
while at the copper electrode the reaction
Cu++ Each
2 e~
Cu.
of these processes can continue only if the stream of negative electrons, or atoms of electricity, can flow from
the zinc to the copper, while the positive and negative ions in the solution migrate towards their respective poles. For every mole of zinc that dissolves
one mole of copper will be deposited and two faradays of electricity (cf. page 132) will travel through the wire. The electromotive force (e.m.f.) between the
electrodes depends upon the difference between the tendencies of
-
Zn +
the metals to become ions, and also upon the relative concentration of the ions in the solution.
If
the concentration of zinc ion
is
so4 ~;
diminished, or that of copper ion is increased, the reaction,
Zn
will
Cu++ = Cu
Zn++,
have a greater tendency to take place, and will give a larger action, Zn + Cu++ = Zn++ + Cu. electromotive force when occurring in an electric battery. If silver ion and silver are substituted for copper ion and copper, we will have a stronger oxidizing agent, a greater tendency to take up the electrons
Fig. i.
Electric cell utilizing the re-
given
force.
off
by the
is
zinc
and a battery of higher electromotive
customary to represent the sequence of the component parts of an electric cell or battery by a simple,
18. It
$56
The
cell just
Ch.
XV
formal scheme.
described could be written:
Zn Zn++ Cu++ Cu
but, since the electromotive force depends upon the concenit is often desirable to be more explicit, for example,
'
trations,
as follows:
ZnjO.l
Jlf-Zn-H-,
0.1
Jf-SO 4
0.1
:
M-SO 4
"
0.1M-Cu++|Cu.
Again, suppose that we wish to obtain electric energy from the oxidation-reduction reaction,
2 Fe++
C1 2
2 Fe+++
CP.
The main
point to remember is that the oxidizing and reducing must not come into direct contact, but the electrons agents
derived from the reducing part of the reaction, the "reducing in this case Fe++ = Fe+++ e~, must flow out of couple,
the solution and through an external circuit, where they can do electric work for us, on their way to the oxidizing agent
which unites with them, in this case by the reaction: C1 2 + 2 e" = 2 CP. This can be accomplished by inclosing the solution containing the Fe+++ in a porous cup which would
permit the migration of ions while preventing gross diffusion or convection. 19. In the preceding case, the reducing agent, Zn, is a metal and the electrons can escape directly from it into the wire of the external circuit; but when using Fe++ as the reducing agent, it is necessary to supply an inert, conducting electrode which can receive the electrons without undergoing any chemical reaction. Any metal not oxidized by FC+++ could be used, but platinum, Pt, is usually preferred. The electrons coming through the external circuit to react with the C1 2 can be led into the solution through a similar inert electrode, e.g., platinum or graphite, surrounded by chlorine gas. The construction of the cell is illustrated in Fig. 2 and can be formally represented, with sample concentrations, by
Pt 0.01
1
Jlf-Fe+++,
0.01 M-Fe++,
0.05 Jlf-CP
0.05
M-K+,
0.05Jlf-Cr|Pt,Cl 2 (latmos.)
22

The
e.m.f. of the cell
all
257
20.
depends upon the concentrations
of
the participating ions as well as upon the pressure of the C1 2 gas. The effect can be correlated qualitatively, with
effect
the
of
changing concentrations
upon
shifting
an
equilibrium. Just as equilibrium for the reaction

2 Fe++
C1 2
2 Fe+++
+ 2 CP
right
would be driven to the
by
increasing the concentration of Fe++ or the concentration or pres-
sure of C1 2 gas, or by decreasing the concentration of Fe ++ + or of

Cl~, so the driving force
Pt
and hence
-ci-
the e.m.f. of the reaction when not at equilibrium would be increased by the same changes in
concentration.
21.
The
of e.m.f.
Fig. 2. reaction,
E,.
.,
quantitative dependence on concentration is given
2 Fe ++
Electric cell utilizing the C1 2 = 2 Fe +
T-I
...
approximately by the formula J * v*
+2
or.
E =E .
0.059
logic Q,
where
pijere,
E is the e.m*i
and pure
of the
cell,
their standard concentrations (1

spliiA*)*
is its e.m.f. with all reagents in molar solutions, gases at 1 atmos-
& is the
number
of electrons transferred in
tbecellreac4apo^ttd jgis the ratio of concentrations, just as it wouM be wrrtteaM" the ^Bttiamum constant equation. Thtts, the e.m.f. of dieciied in the jecediog paragraph is
JE
.
0.5S7
0.
22.
The
fa|r<ic^gen
C3a be used to measure the

of
hydrogati
tern
solution. This consists of a small
plate of platinum,
Ch.
XV
made rough by depositing fine "platinum black" and dipping partly into the solution and projecting by electrolysis, above into an atmosphere of hydrogen. The gas dissolves sufficiently in the platinum to be capable of the reaction, i H 2 = H+ + e~~, and set up a definite e.m.f. If two such electrodes were used, one dipping into 1 Af-H + the other into H+ of unknown concentration, the e.m.f. between the two electrodes could be used to calculate Cz in
,
Fig. 3.
Hydrogen electrode apparatus.
the above formula. It is more convenient, actually, to use a standard calomel electrode, mercury, covered with Hg2Cl2 in 1 M-KC1, in place of the known hydrogen electrode, since we already know the relation between these two. The apparatus is illustrated in Fig. 3. Figure 4 shows several curve types resulting from following
the hydrogen ion concentration, plotted as pH (cf. Chapter XIII, Table 2) against equivalents of alkali added. Such curves throw much light on the processes taking place. HC1, being a strong
acid, keeps the solution at high acidity as long as any of it is present. The concentration of ion drops only one power of ten when
the acid
is
nine- tenths neutralized,
two powers of ten when
it is
0.99 neutralized, etc. There is a sudden rise in pH through the neutral point to strong alkalinity. Acetic acid is a moderately weak
22
259
ion acid and hence the curve begins for a 0.1 molal solution at concentration of 0.0013. As neutralization proceeds the accumulat-
ion coning acetate ion causes a rapid decrease in acidity, the centration becoming 1.8 X 10~5 when it is half neutralized, that is
(Ac~) = (HAc). The steep portion of the curve extends through a much smaller range than was the case for hydrochloric acid. This illustrates clearly why there is a much narrower choice of
0123
Equivalents of alkali
Fig. 4.
Neutralization followed by
means
of a
hydrogen electrode.
and that the best an indicator changing in the neighborhood of pH = 9. Boric acid is a very weak acid and can be neutralized only in a rather alkaline solution. Furthermore, the steepness of the curve at the end of the titration is not very great and even though an indicator were carefully chosen the color change could not be sharp. The precipitation of Mg(OH) 2 from Mg++ requires
indicators for this titration than for the other
results
would be obtained
for
a rather alkaline solution and

of
is
practically complete
on addition
,
of course, requires three equivalents of alkali, but on account of the great insolubility of this substance it takes place in acid solution. The
alkali.
two equivalents of
To
precipitate
A1(OH) 3
beginning of the curve shows an acidity due .to the hydrolysis of A1+++. Aluminum hydroxide dissolves in approximately one
260
Ch.
XV
equivalent of alkali showing that it acts as a monobasic acid and ~ that the principal ion present in the solution is A1O 2 or HjjAlOa".
23. lonization of
in alkaline solution.
water from e.m.f. of hydrogen electrode The e.m.f. of a cell with two hydrogen
electrodes,
alkali of
one
in acid of
known
by one of
of
KG,
known concentration, the other in concentration, the two solutions separated enables one to calculate the concentration
in the latter solution, and the product (H+) (OH"") in this solution is, by aid of the formula in paragraph 21, the
H+
are
ionization constant of water. In practice, the measurements made somewhat differently to avoid potentials at the boundaries of the solutions, but the procedure does not
differ
from the above in principle. This e.m.f. method is more accurate than the conductivity method outlined in Chapter VIII, paragraph 20, because of the great difficulty of preparing absolutely pure water for the latter method. The following values of w have been obtained: C.,
0.114
24.
10~ 14
18
C,
0.58
10~ 14
25
C,
is
1.005
10~ 14
The
electromotive force of a battery
a measure of the
tendency of the reaction to take place, of the chemical affinity of the reaction, a term much used in the development of chemistry,
but also much abused, for it has often been used very loosely. It is only in comparatively recent years that it has been given an exact
TABLE
Reaction
2
AH
AF*
H2 + 1
C1 2 (g) = H+ + H+ + OH~ - H*O

=*
=*
CT + H2
Zn -f H* ~ Ca++ -f.COf
**b
Zn-H-
- 39,940 - 13330 - 36,720

H-
= PbCl 2 Fe+++ + Ag - Ag+ + Fe++
CaCOs
C1 2 (g)
2,780 85,390 14,306
31,370 19,12Q 34,980 10,920 75,050

1,220
definition.
On
this
account
it is
desirabte to substitute the
term
free energy for affinity. The electromotivefoit* of the copper-sine cell when normal solutions o^copprtr amf zhie satiates- are used is
about 1.09 volta^ Tfeefoee energy erf the reaction at these concentration* ir the wosfe it caff do, which wonki be l. X 2 X 96,540 s. or joules, per mole of reacting* substances.
27
261
Table 2 shown on P3ê 260 illustrates the degree of correspondence between free energies, AF, and heats of reaction, AH.
25. Cleaning Silver. The reaction between zinc and silver may be utilized in cleaning the tarnish from silverware. The tarnish consists of silver sulfide, Ag2 S, and though this
ion
gives but a small concentration of silver ion, the free energy of the reaction is still sufficient for it to take place quite readily. If, therefore, a piece of zinc (aluminum will also
serve)
silver,
is
placed in electrical contact with a piece of tarnished both dipping into water containing a little salt to
it
render
conducting, and hot to increase the speed of re-
action, the following reaction takes place over the surface of the silver:
Ag 2 S
2 e
Ag
S~,
the electrons being furnished by the zinc. The sulfide ion liberated would, of course, undergo hydrolysis. The silver is thus restored instead of being rubbed off as in ordinary
polishing. 26. If a solution
it
containing the ions of two metals
is
possible to reduce at the cathode, first electrolysed, the ion of the nobler metal, and afterwards that of the baser
is
metal,
is
by proper regulation
of the electromotive forced It
electrolytic, sqpa**tfoa of different possible thus to metals, which is to be preferred r iflfff*attiy cases, to the ordinary methods of separation based upon the precipitation of in-
make an
soluble coropciwidi* Tfee metaf is deposited
upon a weighed then washed, first with water, then with platimrm eaffc&de, metfrji akofiol, or with ethyl alcohol followed by ether, dried
and irweighed.
271 Efectrolytk Refining.
refilled
An impure
it
very cheaply by making

its
metal can often be the anode in a solution of
one of
metal.
own salts anfd" transferring it to a cathode of pure Any nobfef metals present in the anode remain behind
unoxidized a#a: "sludge" in a bag around the anode, while any partidfes c*f baser metals coming to the surface as the
262
Ch.
XV
anode dissolves go into solution as ions but are not deposited at the cathode since there are enough ions of the metal
being refined to unite with the electrons coming to the
cathode.
The diagram in Fig. 5 illustrates this process for
copper supposed to contain

the nobler silver and the baser
zinc.
The
silver
remains in
the anode sludge, the zinc re-
mains
ode.
in solution,
and pure
copper deposits at the cath-
The
e.m.f. is practically
the same at the two electrodes,

so that only a very low volt-
age is necessary, and hence the energy COSt is 10W. High purity 5 Electrolytic refining of copper. is particularly important for copper to be used for electric wiring since certain impurities
Water and Acids. When a metal dissolves in water, in alkali, or in dilute acids the substance reduced is usually hydrogen ion. Accordingly, it is desirable to introduce H+ and H 2 into the table previously
given. In attempting to do this we find an apparent discrepancy in the reactions of the metals with hydrogen ion, for iron will dissolve in dilute hydrogen ion, whereas zinc,
if
greatly increase its resistance. 2S. The Solution of Metals in
We
very pure, and especially if wet with mercury, will not. find, however, that this is due to the difficulty which hydrogen has in depositing on a surface of pure zinc or mercury, for if a piece of platinum is dipped into the acid and brought into contact with the zinc, we find that the latter dissolves quite readily. The hydrogen is then deposited on the platinum, the electrons left behind when zinc is converted to zinc ion traveling through the metals to the platinum, where they neutralize the hydrogen ions, changing
them
into hydrogen gas.
If
we
test the solubility of the
29
263
various metals in dilute acids in this way, we find that all those to the left of copper in the table will dissolve, although
lead and zinc will do so only with great difficulty, when pure, and in the absence of some more favorable surface for the hydrogen to deposit upon. The same difficulty is en-
countered in reducing hydrogen ion at certain cathodes, for a higher electromotive force is required to deposit hydrogen at a given rate on some surfaces than on others. A successively
higher electromotive force is required with cathodes of the following substances: Pt (rough), Pt (smooth), Ag, Cu, Sn, Pb, Zn, Hg. Hydrogen thus takes the place given in the more ex-
provided that a rough platinum surface is in electrical contact with the metal dissolving. We see, then, that copper, silver, mercury, and the other noble met271,
tended table on page
not dissolve in acids like dilute hydrochloric and sulunder any circumstances,while lead and the baser metals will dissolve in dilute hydrogen ion, provided that platinum is in contact with the metal, but that lead and zinc, or other base metals if amalgamated with mercury, may dissolve very slowly, or practically not at all. When impure zinc is used, the particles of foreign substances, like iron and carbon, furnish nuclei upon which the hydrogen can deposit with more ease, hence such zinc will dissolve at a reasonable rate. 29. As we approach the top of the table, where the metals become baser, and better reducing agents, the hydrogen ion does not need to be so concentrated in order to act upon the metal, and even the extremely dilute hydrogen ion of water is able to oxidize and dissolve metals like calcium and sodium.
als will
f uric
Aluminum
reaction being
dissolves easily
in
dilute
hydrogen
ion,
the
Al
H+ =
A1+++
+ | H2
If hydroxide ion is used instead of hydrogen ion, although the decrease in the concentration of the latter would tend, by itself, to stop the solution of the aluminum, at the same time the concentration of aluminum ion is decreased very
greatly on account of the formation of the aluminate ion, a
264
fact
Ch.
XV
tion in the
which aids the reaction, and compensates for the reduchydrogen ion concentration. Hence aluminum
will dissolve in alkali as well as in acid.
The same
is
true of
zinc.
The equation
Al
for the
former
2
is
+ OH~ + H O = A1CV + f H
2.
30. Solution of Noble Metals. For the metals to the right of hydrogen in the table a stronger oxidizing agent than hydrogen ion is necessary. This is found, for some, in nitric acid, whose oxidizing action is due to the reduction of nitrogen
can rather than of hydrogen. Copper, silver, and in nitric acid. accordingly be dissolved typical reaction is the following: ~ 2 8 H+ = 3Oi*+ 2 4 2 O. 3 Cu 3
meroy
+ NO +
if
+ NO + H
.
oxidize copper, to SO2 silver, being reduced 3J. When we come to the noblest metals, like gold and platinum, even the oxidizing power of nitric acid becomes insufficient. Instead, however, of seeking a stronger oxidizing
Sujfuric acid,
hot
and Concentrated, can
and mercury,
its sulfur
will
agent, another principle is invoked. The following reaction not take place with nitric acid alone:
3 Pt " + 4 NO +
3
16
H+ =
3 Pt++++
+ 4 NO + 8 H
2 0.
is prone to form a complex acid with PtCl 6 chloroplatinic acid (cf. Chapter 2 hydrochloric acid, XIII, paragraph 20), and hence, if a mixture of hydrochloric and nitric acids, known as "aqua regia," is used instead of the nitric acid alone, the platinic ion, one of the products of the oxidation, is used up sufficiently to enable the reaction to proceed. It is not true, as is often erroneously stated, that the chlorine liberated by the aqua regia 3 CT - C12 NOC1 4- 2 2O) is a (4 H+ stronger oxidizing agent than the nitric acid, for if this were the case chloride ion would not be oxidized by aitric acid. Chlorine is, however, a more rapid âridi/Jng agent, and the
Platinic ion, however,
+ NOr +
effectiveness of the
aqua regia
in doubtle8s,4afte
to this fact as
34

of
265
well as to the formation of the
complex chloroplatinic acid. on gold is quite analogous to that aqua regia Dn platinum. In this case the complex chloroauric acid,
The action
HAuCU,
32.
is
formed.
ion,
Cyanide
CN~, forms such a

;
firm complex with
both aurous and auric ions that when it is present the oxygen af the air is sufficient to oxidize gold the reaction is
2
Au
+ H O + 4 CN- =
2
Au(CN) 2
+ 2 OH~
Phis reaction
tion of gold
is
used in the "cyanide process" for the extracits ores.
from
33. Corrosion.
The
corrosion of metals
.is
by moist
air,
like
the solution of metals in acid,
an electrochemical process.
When
iron rusts, the reaction
Fc = Fe++
e-
takes place at the metallic iron surface, while the reaction
4 e~
+ O + 2 H O = 4 OH~
2 2
takes place at impurity specks in the surface of the iron, or at :he surface of noble metals in contact with it. For this reason,
ron of extremely high purity is resistant to rusting. During rusting, current is conducted through the solution by ions; consequently, rusting is accelerated in solutions of high ionic :onductivity, such as salt water. The ferrous ion produced
by electrochemical action is subsequently oxidized to ferric 3y dissolved oxygen, and precipitates as ferric hydroxide. 34. General Table of Oxidizing and Reducing Agents.
may consider the oxidizing and reducing powers involved n changes other than those between the metals and their ons just considered. We find, for example, that chlorine liberate bromine from bromide ion, and that bromine liberate iodine from iodide ion. Accordingly, we may :onclude that chlorine will liberate iodine from iodide ion. This information may be tabulated in the manner used preiVe
viously for the metals, as follows:
266
Ch.
XV
Weak
\2
Oxidizing Agents
I-
Br2 BrReducing Agents
Strong C1 2 el-
Strong
Weak
By
place of other
the aid of appropriate experiments we may find the common substances in such a table, and also
TABLE
3
Oxidizing-Reducing Couples
combine
it
with the table given in paragraph

construct
3.
IS.
In this
way we can
larger
tables
of
oxidizing-reducing
Table 4 contains some additional oxidizing-reducing couples, which could have been included in Table 3, and are here listed separately merely to avoid overcouples, like Table
35
267
crowding the diagram. For a more extensive list of oxidizingreducing couples, the student can refer to Appendix II of the Reference Book of Inorganic Chemistry by Latimer and Hildebrand, The Macmillan Company, 1952. In Tables 3 and 4 the couples are written with the electrons
on the
the
right; consequently, all the reducing agents
appear on
left,
and
all
the oxidizing agents on the right. Since the

TABLE 4
Oxidizing-Reducing Couples
couples are arranged in decreasing order of the readiness with
which electrons are liberated, the most powerful reducing agents are found at the top of the tables and the most powerful oxidizing agents at the bottom. When any pair of couples is combined to give an oxidation-reduction reaction, that reaction will occur spontaneously for which the upper reaction proceeds from left to right as written, while the lower reaction proceeds from right to left. 35. Substances That Can Act Both as Oxidizing and Reducing Agents. For any element having more than two oxidation states, the intermediate oxidation states are susceptible both
268
Ch.
XV
and to reduction. Such a substance appears at two places in the table, once when it acts as an oxidizing agent and once as a reducing agent. Among the most familiar of
to oxidation
HNO
like
such substances are hydrogen peroxide, the halogens, L, Br2 and Cb; and 2
;
,
HO
2
many
nitrous acid, metallic ions
Cr+++, Mn+++. The way in which these react depends, of course, upon the substances with which they are mixed. Nitrous acid, for instance, will oxidize iodide ion to iodine, but will reduce permanganate to manganous ion. 36. The positions of the oxidizing-reducing couples in Tables
Sn+ +, Fe++, Cu+,
Hg2 ++,
3 and 4 are strictly valid only if all reagents are in their standard concentrations. The relative positions can be shifted
in concentration. According to the table, for exone might infer that the following reaction would occur: ample,
by changes
Ag+
I-
= Ag
I2.
This would undoubtedly take place if Ag + and I~ could act upon each other at ordinary concentrations without precipitating insoluble Agl.
The same
applies to the action of
H2S
on Ag+.
37.
in
The hydrogen
cases.
ion concentration affects the equilibrium
many
For example, the reaction

I2
SO 2
+ 2HO =
2
SO 4
2 I-
+ 4 H+
proceeds readily in dilute solution. It will be seen, however, that by diminishing the amount of water present and increasing the relative amount of acid the equilibrium is shifted in favor of those substances on the left, and, as a matter of
fact,
concentrated sulfuric acid readily liberates iodine from Similarly, the following reaction accords with in the table of the substances involved the positions
solid iodides.
:
Cr2 O 7
and
in
6 Cl-
14
H+ =
Cr+++
3 C1 2
+ 7 H O,
2
The
concentrated acid the reaction proceeds in this way. + used large amount of up, however, indicates that
the equilibrium would be enormously affected by changing its concentration. In fact the reaction proceeds in the other
38

chromium being by the equation:
Cl~
269
direction in alkaline solution, the and the chlorine reduced, as shown

2
oxidized
Cr0 2 -
CIO-
+ 2 OH~ =
CrO 4
~ + H O.
2
Although
this is apparently
very different from the preceding

the
equation, it involves reduction steps.

38. Oxidizing
essentially
same oxidation and

There are 2 O2, which would
Power and Speed

like
of Oxidation.
hydrogen peroxide, have great oxidizing power if they could react rapidly enough. It is important to distinguish between an oxidizing agent that is "strong" because it is rapid, and one which is strong but slow. Thus iodine will often react more rapidly than chlorine, and hence produce more oxidation in a given time.
Its true oxidizing
some substances,
by the
fact that
it
power, however, is much less, as shown will not oxidize ferrous ion completely,
whereas chlorine
will.
The oxygen
acids,
like
nitric
and
sulfuric acids, are not rapid oxidizing agents.
This seems to
be connected with the fact that they are highly ionized. Nitrous acid, which is not a stronger oxidizing agent in the
true sense of the term, is nevertheless a much more rapid oxidizing agent, and is, at the same time, much less dissociated.
As we compare the oxygen
acids of chlorine, we find that while their reactivity as oxidizing agents decreases in going from HC1O to HClOa, their strength as acids increases greatly.
In a reaction such as the following:
C10 3
+H
Cl-
S0 4
+ 2 H+
although hydrogen ion appears, whence we might expect it to be favored by decreasing the concentration of hydrogen ion, as a matter of fact it will not take place unless the solu-
may infer from this that C1O.3~ is strongly acid. and a large amount of H+ must be present very unreactive, in order to give a certain amount of the undissociated strong
tion
is
We
acid,
HC1O 3 which
,
is
reactive.
With HC1O, however,
reduc-
tion to Cl"" will take place rapidly without adding B+, because undissociated HC1O is such a weak acid that most of* ft
270
in
Ch.
XV
The difference between nitrous be explained similarly; the latter, being a strong acid, must be rather concentrated in order to give enough undissociated molecules of HNOs to react rapidly. In general, when substances react slowly their true place in the table may not be apparent from their ordinary reactions, and the place assigned may not correspond to a reeven
neutral
solution.
and
nitric acids
may
versible reaction. 39.
The
it was by controlling
Solution of Insoluble Sulfides. In Chapter XIII shown how certain metallic sulfides could be separated
the hydrogen ion concentration, and it was pointed out that there is a group of sulfides so insoluble in water that even moderately concentrated hydrochloric or sulfuric acids will not sufficiently remove the sulfide ion,
the metallic ion concentration large. To dissolve such sulfides it is necessary to remove the sulfide ion more
,
to
make
completely. This
into
is
possible
by the use
of a strong oxidizing
agent, usually nitric acid,
S or even SO 4
solubility
acid, accordingly, will
which changes the S completely Moderately concentrated hot nitric dissolve CuS, I^Sa, PbS, and Ag2S.
.
The
dissolve
of mercuric
is
however, that nitric acid

it
so extremely low, without effect. To practically

sulfide
is
aqua regia is necessary, the effectiveness of which depends upon the greater speed of reaction of chlorine as compared with nitric acid, and also upon the presence of the chloride ion, which unites with the mercuric ion to form
undissociated mercuric chloride. The aqua regia thus attacks both constituents of the mercuric sulfide instead of only one. 40. Lead Storage Battery. Other reactions besides the simple change between metals and their ions can be utilized in generating an electric current. A very important one is
that occurring in the lead utilized is the following:
storage
battery.
The
reaction
Pb
+ PbO + 4 H+ +
2
SO 4
PbSO 4
+ 2 H O.
2
It is carried
out so that the oxidation of the lead to lead sulfate,
Pb
SO 4
= PbSO 4
2 e~,
43
271
takes place at one electrode and the reduction of lead dioxide to lead sulfate,
PbO 2
takes
+ 4 H+ + SO
2 e~
= PbSO 4
+ 2 H O,
2
place at the other electrode. The electrons travel through the metallic part of the circuit from one electrode to the other. To charge the cell the reaction is reversed by
sending a current through the cell in the opposite direction From the equations it may be seen that the more concentrated is the acid the more is the equilibrium shifted in favor
of
PbSO 4
hence the larger the free energy of the reaction

force of the cell. There are other conhowever, which argue against too concentrated
and the electromotive

siderations,
an
acid.
nickel-iron storage battery utilizes the following reaction, taking place in alkaline solution:
41.
The
NiO 2
The
and
+ 2H
+
2
Fe = Ni(OH) 2
+ +
Fe(OH) 2
electrode reactions are
NiO 2
+ 2HO+
2
e~
= Ni(OH) 2
Fe(OH) 2
OH~,
Fe
42.
+ 2 OH- =
2 <r.
The dry
cell consists of
a zinc can containing an elec-
chloride absorbed in a porous solid, a carbon electrode surrounded by manganese dioxide.

trolyte of
ammonium
and
The
electrode reactions are
e~
+ Mn0 + NH + + 2 H O
2
NH OH +
4
Mn(OH) 3
and
Zn = Zn++
2 er.
43. Electrode Designations. Confusion often arises in the use of the terms cathode, anode, and positive and negative, as applied to an electrode. Their meaning and proper use may be explained as follows. 'Cathode* and 'anode" refer to processes which occur
1 ' '
at the electrodes,
and depend on the direction of the current.
272
Ch.
XV
(a) The anode is the electrode at which oxidation occurs, the cathode the electrode at which reduction occurs. In speak-
ing of electrochemical oxidation

used.
(b)
and reduction, the terms "anodic oxidation" and "cathodic reduction" are sometimes
The
electrons flow from the anode, through the external
circuit, to
the cathode.
(c) The positive ions (cations) in the solution migrate to the cathode, and the negative ions (anions) to the anode. 44. These definitions hold regardless of whether the proc-
esses are occurring spontaneously,
as in a battery, or are being brought about by a stronger external e.m.f. The application of the terms to the copper-zinc cell, described in
paragraph
is
17,
on discharging through an external resistance
as follows:
AAAAAA/
Zn
anode
cation
oxidation
Suppose, however, that electrons are forced "uphill" in the other direction, by an external direct-current generator with
a higher
e.m.f. The designations anode interchanged, as follows;
and cathode are then
anode
45.
The
"positive" or "negative" sign of the electrode should
always
refer to the potential difference. In the cell just dis-
cussed, electrons are always at a higher negative potential on the zinc than on the copper, regardless of which way they are " " flowing. Thus, it is possible to label the zinc electrode
46

"
273
and the copper electrode + ." In the lead storage battery, the " " and the lead dioxide electrode lead electrode is stamped " + ," and these designations are correct whether the battery
is
being charged or discharged. Because of the internal resistance of a
cell,
and
of polariza-
the potential difference across the cell does vary somewhat, depending on the direction and magnitude of the current flowing. For instance, the
tion
phenomena
at
its
electrodes,
voltage across a typical dry cell, such as is used in flashlights, is 1.55 volts when no current is flowing; when the cell is discharging, at a current of one-tenth ampere, the voltage is 1.52;
to force a current of one-tenth ampere through the cell in the opposite direction requires 1.60 volts. The potential of a cell is
customarily measured with no current flowing. It is convenient to read the sign of each electrode of a cell from the appropriate oxidizing-reducing couples in Table 3
or 4: the upper couple always corresponds to the " ." trode, the lower couple to the
" "
elec-
46. The chief cause of misunderstanding arises from the convention regarding the sign of a single oxidizing-reducing couple. When a piece of zinc is dipped into a solution contain++ a few zinc atoms ing Zn go into solution as ions, leaving their electrons behind in the metal. When the potential of the
,
electrons
becomes
sufficient,
have a
fixed difference of potential
no more ions can escape and we between the zinc and the
solution, the former negative, the latter positive, as illustrated in Fig. 1. The question then arises, shall we designate this potential difference as positive or negative? The answer has to
be quite arbitrary, since all we are observing is a difference. It will depend on whether we are standing in imagination on the zinc electrode or swimming in the solution. In the one case we would call it negative, in the other positive. It is as if John Doe had borrowed a dollar from Richard Roe. Is it a credit or a debit? That depends on whether you are Mr. Doe or Mr. Roe. It is, perhaps, unfortunate that the ordinary convention is to give the sign as that of the solution, for most of us stay
274
cell
Ch.
XV
outside the
and have to decide which electrode to connect
to the rest of the circuit, but the student who understands the convention and the chemical processes determining where
the electrons are going to be liberated from the solution should be able to think out each case correctly.
47.
There
is
no need to be confused by the engineering
practice of referring to electric currents in wires as "positive currents." This is merely a convention. Of course, the real current consists of electrons flowing in the reverse direction,
as has been demonstrated directly by the following experiment: horizontal coil of wire was set oscillating as a torsion pendu-
lum, and an electric current passed through the
coil,
the
direction of the current being reversed each time the coil reversed its direction of rotation. The direction of the current
could be chosen either to increase or to decrease the amplitude of the oscillations. From the results of this experiment it
was
possible to
current-carrier,
compute the ratio of charge to mass of the and the value obtained was 1.73 X 10 8 couthis ratio for the
electron
lombs per gram. The accepted value of 8 is 1.76 X 10 coulombs per gram.
Exercises
1.
In the following reactions state which elements are oxidized

:
and which are reduced

2
Zn
2
2.
Ag+ + Zn = 2 Ag + Zn++; Ag+ + Cl- = AgCl; OH- H O = HZnO - H

2
Hg+
HgCl 2
+ + + H S = HgS + Hg + 2 H+; + Sn++ = Hg Cl + Sn++++ + 2 CK

2
2
;
Write equations
for the following reactions: zinc plus chlorine
to give zinc ion plus chloride ion; stannous ion plus bromine to give stannic ion plus bromide ion; ferric ion plus stannous ion to give ferrous ion plus stannic ion; hydrogen sulfide plus iodine to give sulfur plus hydrogen ion plus iodide ion cupric ion plus iodide ion to give cuprous iodide (ppt.) plus iodine.
;
3.
Write equations
for the reactions
between:
(a) cupric
oxide
and hydrogen; (b) cupric oxide and hydrogen ion; (c) cuprous oxide and oxygen; (d) magnesium and hydrogen ion; (e) cupric
275
ion and zinc to give copper; (/) copper and cupric ion; (g) silver ion and zinc. State in each case which elements are oxidized and which are reduced.
4.
Complete the following incomplete equations:

(a)
(b)
(c)
(d)
(e)
(/)
(g)
(*)
(i)
+ -NOr + Ag = Ag+ + NO; + H S = Mn++ + S; H+ + NO - + CuS = Cu++ + SO ~ + H+ + NO 3" + Zn = Zn++ + NH + Bi(OH) + HSnOr = Bi + HAuCl + Fe++ = Au + S + + =S S O + Cla -= SO -+ CIO- + AsO = AsO +
H+
MnO
NO;
5.
6. the metals given in the table on page 266, construct the battery that would give the greatest electromotive force.
7.
What From
is
meant by "noble" metals and "base" metals?
8.
Explain how contact with zinc protects iron from corrosion. How can you tell whether a metal will dissolve in any of
the following reagents: water, hydrochloric acid, nitric acid, sulfuric

acid,
9.
sodium hydroxide?
How
is
the oxidizing power of
H+
affected
by
its
concentra-
tion?
10.
11.
(a)
Explain the cleaning of silver by zinc or by aluminum. would you prepare each of the following: Br- from Br 2 (b) HC1 gas from C1 2 (c) I 2 from Nal (d) PbCrO 4
How
from Pb and CrCl 3 (e) Fe from FeCl 3 (/) Fe(OH) 2 from Fe; (g) Fe 2O 3 from FeSO 4 (h) Mn(OH) 2 from MnO 4~; (i) Hg 2 Cl 2 from HgCl 2 (J) Hg from HgCl 2 ? 12. What new substances, if any, would be found and in what amounts upon bringing together the following substances? All ions are in water solution
;
(a)
(b)
(c)
Ag+ (1 mole), Cu (1 mole) and Zn Ca (1 mole) and Cl~ (1 mole);
(1
mole);
(d)
(e)
C1 2 (1 mole), Br~ (2 moles) and I" (2 moles); Fe (3 moles), Fe+ ++ (1 mole) and Zn++ (2 moles); Zn (1 mole), 1 2 (2 moles) and Ag (1 mole).
substance will be present and, if in solution, at what approximate concentrations, in the following cases? (a) 1 mole of FeCl 3 4 moles of SO 2 and 10 moles of HC1 are mixed in 10 liters of water.
13.
,
What
276
(b)
1
mole of
Ch.
XV
(c)
2 S is passed into 2 liters of a solution containing 0.5 mole of CuCl 2 and 1 mole of HC1. 0.2 mole of C1 2 is passed into 1 liter of a solution con-
taining 0.5 mole of
KI and
0.5
mole of KBr.
14. From your knowledge which the determining elements can assume, state which of the following substances are capable of acting as oxidizing agents, which as reducing agents (or both) and give the substance which each will probably form when so acting: (a) Cl~, (b) H 2 S, (c) SO 2 (d) H 2SO 4 to A1+++, (/) H+, (g) H 2 2 (*) F 2 (i) F-, (j) Ag+ (*) 2 (/) Hg 2++.
of the oxidation states
15.
Which
(1)
(2) (3)
of the following
agent, (b)
a reducing agent,
changes would require (a) an oxidizing (c) some other type of reagent?
(4)
(5)
I2
Sn(OH) 2 to Sn++++; HSnO 3-toSn++++; CIO- to C1-;
to
2
IO 3-, S to SO 4~.
4.
16.
in
A certain metal will

Cu + +
a solution of
17.
dissolve in dilute or not? Explain.
H SO
2
Will
it
dissolve
Plan an experiment to determine whether Fe+ + or I" is the 4"*"* with stronger reducing agent. (Fe++ on oxidation becomes Fe a change in color.)
18.
Plan an experiment to determine whether F~ or Cl~ gives

electron
up
its
more
readily.
State what electron change takes place (a) when metallic calcium dissolves in water, (6) when magnesium burns in air.
19.
20.
The
(a)
(6)
(c)
following reactions are

2 2
known
;
to occur as read from
left to right:
(d)
Fe+++ + 2 I- = 2 Fe++ + I 2 Bi- + C1 2 = 2 Cl- + Br 2 2 Fe+++ + Sn++ = 2 Fe++ + Sn++++; Cl + 2 Fe++ = 2 Fe+++ + 2 C1-.
;
What can you
conclude from these data alone about the occurrence
of the following reactions? Br 2 = I 2 (a) 2 I(ft)
(c)
(d)
+ + 2 Br~; + 2 Fe+++ = 2 Fe++ + Br C1 + Sn++ = Sn ++ ++ + 2 Cl, Sn ++ + I = Sn ++++ + -2 I~. Explain your answer.
2
Br~
2
Sketch the arrangement of a battery in which the reaction between Zn and C1 2 is used to generate an electric current; (b) From which electrode will the electron stream flow in the wire? (c) How will the e.m.f. of the cell be affected by changing the pressure of
(a)
2L
C1 2 ? Justify your answers.

22. Construct
277
an
electric battery to utilize the reaction
14
H+
Zn
Cr 2
Zn++
Cr+++
+ 7 H 0,
2
and write the equations

23.
for the separate electrode reactions.
An
electric cell is constructed
a solution of
ZnSO 4 and an
by placing a zinc electrode in iron electrode in a solution of FeSO 4

.
The
solutions aie separated by a porous partition, (a) Write the reaction which takes place when the two electrodes are connected by a copper wire, (b) In which direction will the negative electrons
flow through the wire? through the solution?
(c)
In which direction will the
SO 4
move
24. battery is composed of an electrode of Zn dipping into a solution of ZnSC>4 contained in a porous cup. This cup is surrounded by a solution of Fe 2 (SO 4 )3 and FeSO 4 and in the latter is a carbon rod to serve as an electrode, (a) Write the equation for the reaction occurring when the cell discharges; (b) how would the electromotive force change with increasing concentration of (a) ZnSO 4
, ,
(b)
Fe,(S0 4 )i,
the
(c)
FeS0 4 ?
Zn/Zn ++ /Ag+ /Ag, what weight g. Zn dissolves?
of silver will
25. In
cell
deposit
when 0.654
26. Which of the following oxidizing agents are stronger in the presence of 0.1 7V-H+ than in the presence of 0.01 .AT-H*, which are weaker, and which are unaffected by changing concentration of H+?
(a)
Fe+++,
(b)
I 2,
(c)
I0 3-
(d)
Mn(V,
(c)
Ag+. Justify your
answers.
passed through a solution containing 0.01 Jkf-CuCU, using inert graphite electrodes. Write equations showing what occurs at each electrode.
27.
electric current is
An
0.01
Af-KBr and
28.
What
constituents of an electric
cell is it essential
to keep
out of direct contact with each other?

29.
An
electric battery is
made by immersing an
electrode of
iron
of copper oxide in a solution of sodium hydroxide. In the chemical reaction which produces the current, which sub-
and one
stance is (a) the oxidizing agent? (b) the reducing agent? (c) Write the equation for the reaction, (d) How would increasing the concentration of the sodium hydroxide affect the electromotive force of the cell? (e) If heat is absorbed by the cell as it generates a current, would a rise in temperature increase or decrease the electro-
motive force?
30.
Ag
An electric cell consists of an electrode of silver, coated with O, another of metallic aluminum, both dipping into 2 Af-NaOH.
278
Ch.
XV
Write the equations

the total cell reaction. to 3 Jlf-NaOH?
31. Explain the
in the voltage of
for the separate electrode reactions and for would the e.m.f. be affected by changing
How
changes in the density of the electrolyte and a lead storage battery that occur as the battery
discharges.
32. A cell is constructed with an electrode of zinc dipping into a dilute solution of zinc sulfate at the bottom of which is an electrode of mercury covered with a precipitate of Hg 2 SO 4 (a) Write the
.
equation for the total reaction occurring as the cell discharges. = 65.4) would have to dissolve (&) How many grams of zinc (Zn to yield a current of 0.1 ampere for 10 minutes?
33.
When
an excess of
|
CN~
is
is
added to both
!
sides of the cell

|
Cu Cu++, SO
the direction of the current
this fact?
Zn++,
SO
Zn,
reversed.
How
can you account for
34. What can you conclude regarding the migration of cations and anions in the case of a cathodic reduction of an anion, such as C1O 3-, CrO 4 or MnOr?
,
CHAPTER XVI
THE CONSTITUTION OF THE

1.
ATOM
search for the elementary particles constituting as old as science itself. Steadily the size of the supposed ultimate building blocks has decreased until today we speak freely of the structure of the atoms themselves (which were the main elementary units of a generation or
The
matter
is
two ago). At present only one

is
of the particles in the atom to be complex itself and we have (the nucleus) supposed reason to believe that we have reliable information even
its structure. However, it seems certain that the search continue almost indefinitely even beyond our present advanced stage. It appears probable, though, that as we proceed to more fundamental analyses our present picture of the atoms themselves will be altered little in a practical way, because of our almost complete success in explaining the known chemical properties (i.e., compound formation, etc.). In other words, the one particle in the atom known to be complex, the nucleus, has little effect on the properties of the atom as a whole. This does not detract from the importance of continuing the search, however, for we still have the great cosmological questions to answer: "How was our earth and, in fact, the whole universe made?" "What is the probable future of the universe and in particular the solar system?" "What is the source of the tremendous amount of energy emitted by the sun and other stars?" and numerous other problems. On all of these the properties of the atomic nuclei appear to have immediate bearing, as we shall see briefly later in this chapter. Also, we should remember the well-known fact that very practical results sometimes are obtained from the most fundamental researches in pure science, for example, the uses of X-rays and radium in medicine.
as to
will
279
280
2.
The
Structure of the Atom.
Ch.
XVI
Near the end
of the nine-
teenth century laboratory electrical technique had developed to a point where it was possible to measure electrical forces easily and to produce rather high energy spark discharges
Immediately several fundamental discoveries were made. Among these were the following. When an electric discharge is sent through a highly evacuated tube provided with sealed-in electrodes, there is given off from the cathode a characteristic discharge called cathode rays. Unlike light, these rays are almost entirely stopped by the glass walls of the tube, producing a fluorescence upon the glass where
conveniently.
they strike. A screen of fluorescent material like zinc sulfide, put into the tube in the path of the rays, shows a brilliant fluorescence, very useful in studying these rays. They are deflected from a straight path by either a magnetic or an electric field, in such a way as to indicate that they consist of streams of negatively charged particles, moving with great velocity, which have been called electrons. 3. By measuring the extent of this deflection by both kinds of field, it has been possible to calculate the ratio of the charge on each electron to its mass, and also the speed of the electrons. It is evident that some such calculation should be possible, because any moving body can be deflected from a straight line by a known force to an extent dependent
if
speed. It obviously takes more force to deflect a swiftly moving bullet than a slowly moving golf ball, and still more force to deflect the heavy shell of a big gun.
upon
its
mass and
its
The
result of these
measurements and
calculations, carried
out by J. J. Thomson, shows that the speed of the electrons ranges from 10,000 to 100,000 miles per second, and it has
become possible to accelerate electrons nearly to the limiting speed of light, which is 186,000 miles per second. The ratio of the charge to the mass of the electrons is found to be 1840 times the corresponding ratio for a hydrogen ion,
recently
which is 96,500 coulombs per gram. Therefore, either the mass of the electrons is less, or the charge is greater than that of a hydrogen ion. Now it has been found that the charge
4
is
CONSTITUTION OF THE ATOM
281
the same (though opposite in sign), hence we are led to the conclusion that the mass of the electron is of that of the hydrogen ion, the smallest particle of matter previously
TsW
known.
The discovery
atoms may
the
electrons
of the electron provided a unit with which be constructed, and the fact that the nature of
composing the cathode stream is entirely of the nature of the cathode used, as well as independent of the residual gas in the tube, indicates that atoms of all substances contain the same kind of electrons.
4. Isotopes. In addition to the electrons liberated by all substances in a spark discharge, there are produced positively charged heavy particles of different masses for each element
or compound. For example, if the noble gas, krypton, is placed in the discharge tube, six heavy, singly positively
charged particles, six doubly charged, and perhaps even six triply charged will be produced (the relative intensities of the groups with different charges depending on the violence of the discharge and the pressure of the gas). When the masses of the particles are measured in the way described above for the electron they are found to be 78, 80, 82, 83, 84, and 86, the same six appearing in each group and the relative numbers in each of the three groups being exactly the same. The interpretation is that the element, krypton, is a mixture of six different atoms having the different weights given but the same tendency to become positively charged in the discharge (i.e., the same tendency to lose electrons).
The
are determined
abundances of the different atoms, called isotopes by direct measurement of the relative numbers in the different charge groups and are found to be:
relative
Kr78 0.35%; Kr80 2.01%; Kr82 11.53%; Kr83 11.53%; Kr84 57.11%; Kr86 17.47%;
, ,
,
giving an average of 83.7 for the weight of the average Kr atom. (This method of determining atomic weights has come to be as accurate as the older method of measuring out a gram-
atom
of element
and weighing
it.)
Similar experiments on the
282
Ch.
XVI
other elements have shown most of them to be mixtures of two or more isotopes, as shown in Table 1. We notice that even hydrogen has two isotopes, the ordinary isotope of mass one and a rare one of mass two, called deuterium whose symbol is D. In this case the masses
differ
we
two-fold, a larger factor than in any other case, and are in an excellent position to decide whether the mass
by
role in the chemical properthe atom. Table 3 shows the properties of a series of compounds of the two isotopes of hydrogen. Evidently the mass effect is small even in this case so we conclude that the
of the
atom plays a fundamental
ties of
mass of an atom is not what determines its chemical properties. 5. Ordinary oxygen contains small amounts of the heavier 17 and O 18 as shown in Table 2. The mass of the isotopes O
,
lowest isotope is set as 16.000, as is desirable in the study of the nucleus; the mass of the natural mixture is 16.0044. However, long before isotopes were discovered, chemists
adopted 16.000 as the atomic weight of ordinary oxygen. We are thus confronted with two slightly different atomic weight scales, now called the "physical" and the "chemical,"
related as follows:
Physical
scale
Chemical
scale
16
isotope
Ordinary, mixed oxygen
16.0000 16.0044
1.0081
1 .0083
Hydrogen,
Ordinary, mixed hydrogen
15.9956 16.0000 1.0079 1 .0080
At about the same time that the experiments described above on spark discharges through gases were begun, it was
that certain of the elements spontaneously emit radiations, among which are heavy high velocity particles called alpha particles, of double positive charge and atomic weight 4, which we now know to be helium atoms which are
discovered
lacking
two
electrons.
By
virtue of their high energy,
it
was
possible to detect these bodies one at a time and to record their progress through matter until they had lost most of their energy through collision with ordinary atoms. (This
TABLE
Stable
and Long-Lived
Isotopes of the Elements
283
284
TABLE
Relative
2
Ch.
XVI
Abundance
Mass
1
of Certain Isotopes
Element
no.
Relative
abundance
H
Li
99.98 0.02
7.5
6
7
10
11
92.5 18.4
81.6
O
Ne
16 17 18
99.76 0.04 0.20
20
21 22
90.00
0^7 9^3
75.4
Cl
K
Cu
Zn
35 37 39
40
41
24.6 93.38 0.012

6.61
Br
63 65 64 66 67 68 70 79 81
70.13 29.87
50.9
27.3
3.9
17.4
0.5
50.6 49.4
occurs after they have traversed between 2 and 5 cm. of ordinary air, the distance varying, of course, with the energy
of the particular alpha particle.) If
TABLE
3
one
fills
a glass cylinder
Comparison of Chemical Properties of the Hydrogen Isotopes
Hydrogen
Relative ionization potentials
of
Deuterium
1.000270
atom
Heat
(arbitrary unit) of dissociation of mole-
1.000000
103,700 calories
cules,
H D2
2,
105,500 calories
which has a movable bottom with moist air and alternately moves the bottom of the cylinder up and down, one sees lines of water droplets form on the down stroke if there is
CONSTITUTION OF THE
ATOM
285
a small amount of some alpha emitting substance such as the element polonium on the wall of the vessel. This beautiful apparatus, called a "cloud chamber/' invented by C. T. R. Wilson, enables one to study the phenomena visually, in an
intimate way.
Figure
on the
1 shows two photographs of such tracks, the one right containing a track having sharp changes of
Track of a-rays
Fig. 1
Track of two
a-rays (enlarged)
as collisions with heavy bodies in the air would cause. The gas laws have taught us how to calculate
direction such
the approximate size of the molecules as well as the number in a given volume under any conditions. Consequently, as
soon as tracks like the one in Fig. 1 were observed, calculations were made showing that the alpha particles must have hit a heavy body in the air only once in passing through several thousand atoms. This showed immediately that the mass of the air molecules must be concentrated in small regions having only about I Q ,QOO> the diameter of the atoms themselves. Also, calculations on the angles through which the alpha particle was deflected showed the mass of the body struck to be the known atomic weight of either oxygen
286
Ch.
XVI
or nitrogen, according to which was involved in the particular collision considered. The startling fact therefore was established that somehow the mass of the atom was concentrated in a very small part of the total atomic volume. This suggested that the light electrons might be revolving about
that in
the heavy, positively charged nucleus in a way similar to which the planets revolve around the sun, which we believe now to be the case.
If a beam of high energy helium gas, the electrons are electrons passed through found to emerge with their energy practically unchanged unless the energy of the electron exceeds a certain minimum value. As the energy of the beam is increased from a value near zero, one finds no slowing of the electrons until a certain
6.
is
The Quantum Theory.
value
is
reached,
when many
of the electrons lose nearly
all
of their energy. This experiment shows that the helium atom is incapable of taking energy in amounts smaller than a
certain
minimum. It is necessary to hit the atom with at amount of energy before anything happens. Similar experiments with the other atoms have given similar
least a certain
results, the particular minimum energies being different for each element. This concept that atoms can take energy in certain definite amounts only, together with its numerous consequences, is known as the quantum theory. 7. Energy Levels. After the atoms in the above experiment have been struck with high energy electrons, they emit light. (This is the mechanism of the familiar neon sign.) The color of this light is found to be definitely related to the minimum energy required to excite the atom, so we conclude that the atom has emitted this "chunk" of energy as light after having taken it from the electron. By using a gas being bombarded with electrons of a wide range of energies and carefully determining the various wave lengths of the light emitted, it is possible to decide not only what is the smallest amount of energy a given atom will absorb, but what the successively larger amounts are. In this way one is able to say what values the energy of any given atom can have. This

set of values,
28?
called the
when
written in increasing order,
is
energy level scheme. Figure 2 represents the scheme for hydrogen, the distance above the bottom line being proportional to the energy values. From 15
the absorption and emission spectra of the atoms, similar energy level
6
schemes have been constructed for

all
-4*5
3
the elements.
closer study of atomic spectra
10
shows that the second quantum level in Fig. 2 is not a single level, but a group of three closely-spaced levels; the third level is a group of five; the fourth level a group of seven, and so on. Moreover, the spectrum of an atom subjected to a magnetic field shows a farther splitting of each of these levels into two or more.lln this way, it is found that the lowest
2
quantum
level
is
made up
of
quantum
closely-spaced levels; the second level is made up of a total

Fig. 2.
of 8 sublevels; the third, a total of 18 sublevels; the fourth, 32; the

fifth, SO.
Energy levels of the hydrogen atom.
These groups of energy levels are sometimes called "shells." Thus, the lowest pair of levels comprises the "K shell" the second group of 8, the "L shell"; the third group of 18, the "M shell"; and so on.
On the basis of certain systematic differences in the spectra to which they give rise, the energy levels within a shell can be farther classified. The names assigned by spectroscopists are s, p, d, and/, from the words sharp, principal, diffuse, and fundamental, which originally had to do with the description of certain series of spectroscopic lines. Thus, the lowest shell consists of
two
5-levels; the
second
shell, of
two
s-levels
the third
the fourth
shell, of
shell,
two of two
s-levels, six ^-levels,

s-,
and six p- levels; and ten d-levels;

/-levels.
six p-, ten d-,
and fourteen
288
8.
The
Ch.
XVI
firmness with which the electrons are held in each
shell increases
the atomic number.

in the
with the positive charge of the nucleus, which is The relation is a simple one: for electrons
of shell, the binding energy
is
same type
approximately
proportional to the square of the atomic number. Consequently, the energy difference between any pair of quantum levels is proportional to the square of the atomic number.
These energy
frequency
it
differences,
which can be measured by the
of
the X-rays emitted
by
fast
the atom
when
it
is
electrons, have made possible to determine atomic numbers with certainty. It has been verified, for example, that tellurium belongs before
subjected to
bombardment with
iodine, despite the fact that tellurium has the larger
atomic
weight. 9. In the normal hydrogen atom, the electron occupies the lowest quantum level, and all the higher levels are vacant. The electron can be 'excited " into one of these upper levels
'
or by the absorption of light. After a short time, drop back to its normal level, with the simultaneous emission of light.
by
it
collision,
will
In the helium atom, which has two electrons, these occupy

the two lowest levels (the two 1 ^-levels) and all the higher levels are vacant. In lithium atom, with three electrons, the two 1 s-levels and the next higher level (which is a 2 s-level)
are occupied. In Table 4 the quantum levels which are occupied by electrons are listed for all the elements.
10.
Though we do not intend here
to consider in detail the
theoretical attack
on the problem of atomic structure, we will of its fundamental features to show that the energy give enough level scheme, including the number of sublevels in a shell, comes
naturally out of the theory. Bohr, in 1913, postulated that the electrons in an atom move in orbits around the nucleus, just as planets move in
orbits around a sun.
The
different energy levels
were supposed
to correspond to orbits of different size, the possible orbits being selected by the additional rule that the angular momen-
tum
of the system
had to be an
integral multiple of a certain
10
CONSTITUTION OF THE
ATOM
289
of
fundamental constant. This model did permit the energy levels hydrogen to be calculated accurately. The "planetary" model was abandoned with the development (in 1925-1928, particularly by Heisenberg, Dirac, and Schrodinger) of the theory of quantum mechanics, which undertakes to calculate not the path followed by an electron in its motion, but the
probability of finding the electron in
any
particular region
of space about its nucleus. Pictures of some of the calculated electron probability "clouds" were given in Fig. 2 of Chapter V.
Although we no longer speak of electron orbits, we have kept the term "orbital" to refer to the probability cloud. The mathematical methods of quantum mechanics are rather complex, but many of the results are quite simple. It turns out that the orbitals of the individual electrons are
described
principal
by four numbers, quantum number, n,
called
is
quantum numbers. The
the
number
characteristic of
1 for the first shell, n = 2 the shell being considered, i.e., n for the second, etc. The second or azimuthal quantum number, 1. It specifies the to n /, can take all integral values from
orbital angular
momentum of the system

d-,
for
;
=
/
0,
momentum is zero
(which give the p-,
(these are the s-orbitals)
for
the angular 1,2, and 3
and /-orbitals respectively) the total angular momentum of the system is \/2, V6, and Vl2 times the fundamental unit of angular momentum. The third or magnetic quantum number, m, which can have all integral values from
/
to
+
;
/,
including zero, specifies the component of the
angular momentum along the direction of a magnetic field. The fourth or spin quantum number, s, can have the value ^
or
it is
so called because each electron behaves in a
mag-
were spinning rapidly, the angular momentum involved being just one-half of the fundamental unit mentioned previously. Let us calculate the total number of orbitals possible in each shell. For the first shell, n = 1 so / and m are both zero; 5 can take either of its two values; thus we are allowed only two orbitals in the first shell. For the second shell, -n = 2, so / can be (giving the 2 s orbitals) or 1 (giving the 2 p orbitals) with
netic field as
though
it
290
/
Ch.
XVI
is 0, 5 can have its two the only possible value for = 1, can values, so there can be two 2 s-orbitals; with I
m
1,
take the three values
1,
0,
for each of
which
can
have two values, giving a
total of six 2
-orbitals.
The
total
number
shell is accordingly 8. Similar
of possible electrons which can occupy the second treatment of the other shells
gives 18 for the third, 32 for the fourth, and 50 for the fifth
shell.
The tendency for an atom with several electrons to have them grouped together into shells, each having a definite number of electrons, is fundamental to the study of chemical reactions. The essential cause of chemical bond formation is the tendency of two or more atoms, each of which has a
11.
valence electrons, to themselves in a way that among as nearly as possible places all electrons in filled shells. For example, two hydrogen atoms combine by sharing their two valence electrons so both electrons can belong to a closed
filled shells, called
few electrons not in
redistribute their electrons
shell of two, at least part of the time.
(We may
think of the
electrons
this
moving around
first
one proton and then the other,
interchange occurring so rapidly that neither proton has time to get away before the electrons move over to
it.)
This
is
one of the two basic kinds of chemical bond and
is
known
as the electron share, or electron-pair or covalent
bond, for obvious reasons. It is represented by placing two dots representing the shared valence electrons between the
bound atoms, e.g., H:H for Kb molecule. The other bond results when an atom (nonmetal) whose valence shell lacks just one or two electrons takes the valence electrons from an atom having only one or two (metal). The result of this transfer is a negative charge on the atom gaining electrons and a positive charge on that losing its valence electrons, and the bond consists of the standard electrical attraction between these charges so produced. For example, a sodium atom having 1 valence electron gives it to a fluorine atom having 7 valence electrons to fill up the second shell on the fluorine atom to its proper value of 8 forming the NaF mole-
13
CONSTITUTION OF THE
: :
ATOM
291
cule represented
electrostatic
+ by Na F or Na F~~. This is known as the or ionic bond because of its electrical character.
It is, of course, not a saturated bond, for the attraction can extend to other neighboring ions. 12. These two bonds differ greatly, in fundamental ways. The electron-pair bond, consisting as it does of a sharing of electrons to close two electron shells, one on each atom, should be broken if the distance between the bound atoms were increased by more than about the thickness of the aver8 age electron shell, a few tenths of an Angstr0m, which is 10~ cm. Furthermore, one would expect the rupture to occur rather suddenly as the distance is increased, much as a cast iron rod breaks if sufficient tension is applied to its ends.
On
the other hand, since the electrostatic bond
is
of the nature
two charged bodies, increasing the distance of separation by a factor of two (about two Angstr0ms) should decrease the bond strength by only a factor of 2 2 or 4, due to the inverse square law of force applying in this case. This makes the electrostatic bond much more elastic in character, and allows molecules with such bonds to be formed and broken more rapidly because the collisions which can lead to formation and destruction do not have to be so exactly right
of an attraction between
,
as in the case of the molecules with electron-pair bonds. In other words, we expect from these considerations to find that molecules with electron-pair bonds can have more definite
structures
may
involve
and that, though no more energy
their formation
and destruction
than for
(in fact, generally less)
those with electrostatic bonds, they will be formed and destroyed less readily due to the exactness with which the atoms
have to be placed. All of these are well-known facts and verify our whole picture. It is interesting that the most essential molecules in living organisms are held together by bonds of the
electron-pair type.
13. Certain
media, such as water, are able to reduce the
acting between charged bodies by a certain factor called the dielectric constant (cf. Chapter VIII, paragraph 2). The dielectric constant of water is 80, so we expect that
force
TABLE 4
The Electron
Structure of the Elements
292
TABLE 4
(Cont'd)
The Electron Structure of the Elements
293
294
Ch.
XVI
molecules held together by electrical bonds will be broken

into their charged fragments when they are dissolved in water or any other liquid of high dielectric constant, the mild collisions occurring due to thermal motions of the molecules in the liquid being sufficient to break the weakened bonds. This is the explanation of the phenomena of ionization we have studied in preceding chapters and gives us an immediate
14.
and
practical test for
bond type.
Intermediate between the two types of bonds just considered, there is a large and important class of molecules
(cf. Chapter V, paragraph 12) in which the electrons are incompletely transferred. For instance, they may spend three fourths of their time on one atom and one fourth on the other,
giving us a bond half of the share type and half of the electrostatic type. These bonds of intermediate type, called
polar bonds, have characteristics intermediate between those discussed above for the pure types. For example, compounds
with bonds of this kind
may
ionize only partially
when
dis-
solved in water, constituting the general class of weak electrolytes. Finally, it must be noted that a single molecule may
have
different types of
bonds
in its different parts, for in-
stance, in
Na2SO 4
the bonds between the
Na and O atoms
S and
certainly are electrostatic while those between the atoms are electron-share bonds.
15.
Examination of Table 4 reveals that A has only 8 electrons in its third shell, which should have 18 when filled. Argon certainly is an extremely inert element, so we are forced to consider why atoms with three shells of electrons
are relatively satisfied when their third shell has 8 instead of 18 electrons. When we consider the courses of action open
A atom, the impossibility of filling the shell by either kind of chemical bonding becomes clear. By complete transfer of electrons, the A atom has the choice of losing 8 or gaining 10, in either case the charges induced after the removal, or
to the
gain, of say 5 electrons, would be so large as to prevent any further transfer. The possibilities through sharing of valence
electrons with other
atoms appear to be
better,
but when we
17
realize that
295
about ten other atoms must be grouped around

fill
the
atom to
the 18
shell,
we
see that this possibility

fitted
is
ruled out because no known ten atoms can be

closely
around
enough to form electron-share bonds, which are particularly sensitive to structural inconveniences anyway. So it becomes apparent that for the larger shells it is not the shell itself which will be filled by chemical bonding, but rather some smaller group within these larger shells. This group is that of eight. It is more stable than any other grouping of electrons
within the
shell,
and, for the reasons presented above, as-
sumes the role for bond formation played by the shell as a whole in the lighter atoms. In fact the whole principle of bond formation can be restated in the form that bonds are formed
to complete outer shells or octets. 16. The Periodic System itself affords
in the larger shells.
abundant
justifica-
tion for this treatment of the octet as a particularly stable
electron
For example, when one more added to the argon structure to form potassium, instead of going into the third shell, which needs 10 more, it prefers to go into the empty fourth shell. This continues
subgroup
is
when the next electron put form Ti) sometimes goes into the third shell. This happens repeatedly until the third shell is finally filled in Cu, which has one electron in the fourth shell. The possibility of having the electrons in either of two shells leads to an atom's having more than one possible set of valence electrons and therefore two or more sets of chemical properties. This, of course, is known to be true of just these elements we have
till
the fourth shell has three,
in
(to
discussed
filling of
and
also of those involved in the

fifth
same way
in the
the fourth shell while the
has only a few electrons
in
it.
ATOMIC NUCLEI
paragraphs it has been nucleus which is of to the ordinary chemical characteristics practical importance
17. Introduction. In the preceding
shown that the only property

of the
of the
atom
is
the positive charge. However,
we know much
296
Ch.
XVI
more about the
nuclei than the values of their charges
and
we
shall consider their general properties briefly in this sec-
tion.
present, approximately 1500 nuclei are known. Of these, 282 are stable, or last at least as long as 10 6 years, and the
At
remainder decompose at various rates to form the stable nuclei. It seems probable that a few more stable nuclei will be found and almost certain that additional unstable ones will appear, so we may expect the total somewhat to exceed 500 in the rather near future. 18. The principal constituents of the nuclei now appear to be the proton and the neutron. The proton is the nucleus
1.3
10
20
30
40
50
60
70
80
90
100
Atomic number, Z
Fig.
hydrogen atom, has a mass of 1.00755 and a single positive charge. The neutron has no charge and weighs 1.00894. These particles apparently exist together in the
of the ordinary
nuclei in a
way
exist in a small
quite analogous to the way the molecules drop of liquid, or perhaps a very small crystal.
The
correspond to what would be from the masses and sizes of the neutron and proton expected if they were packed closely together. Also, the observation from collision experiments that only at relatively short distances (of the order of the diameter of the average nucleus,
densities of the nuclei
cm.) do the constituents strongly attract each other leads us to expect that they must be extremely close together in order to account for the great stability of the ordinary
10~~
12
nuclei.
The nature
of the attraction appears to be such that
20
CONSTITUTION OF THE
ATOM
297
the most stable structures tend to have about equal numbers of neutrons and protons. This gives the well-known rule that the atomic weights of the elements are nearly twice the atomic numbers. However, as the nucleus increases in size the strong repulsive forces acting between the protons at these short
distances (such electrical forces vary as the square of the reciprocal of the distance of separation) require more neutrons to bind them together. Figure 3 shows this.
the nuclei are heated by bombardment with high energy particles, such as protons, neutrons, alpha particles, the nucleus of the heavy hydrogen isotope (called
19.
When
the deuteron), or high energy light (called gamma rays or hard X-rays) the energy apparently is distributed rather rapidly over the system as a whole and results in an evaporation process causing certain simple particles, such as neutrons, protons, deuterons, or alpha particles, to boil off until the
system has cooled. These energies correspond to nuclear temperatures of several hundred million degrees. Loss of the energy by the emission of gamma radiation also occurs. There are differences in mechanism among the various processes which lead to systematic differences in the rates at which
these emissions occur.
rate of the evaporation process decreases very with the temperature of the nucleus, so that if the sharply cooling process following bombardment with high energy particles happens to leave the nucleus in a slightly warm
20.
it may if there is only enough energy to evapoone particle but not two, or two particles but not three, etc.) the rate at which it cools may become very small and may increase the time of cooling from about 10~ 13 seconds
The
condition (as
rate, say,
(for the rapid evaporation processes following bombardment) to 10 12 years. These slower processes of course are almost
in a different class, experimentally, because they may be detected at convenient times after bombardment rather than
requiring
set of
investigation during bombardment. The whole phenomena associated with these slower transforma-
tions
is
known
as radioactivity.
S98
21.
Types of Radioactivity.
to
Ch.
XVI
When
nuclei with the ratio
of neutrons
protons somewhat higher than the
stable
value are formed in a state not too highly excited, the return to the stable state does not occur through the evaporation of a neutron, but through the conversion of a neutron into
a proton in the nucleus with the emission of a negative electron, and possibly other radiation whose existence we suspect
but have not activity. For neutrons and neutrons and

trons,
confirmed. This process is known as beta radio24 nucleus has 13 example, the unstable Na 24 11 protons, while the stable has 12 only
Mg
12 protons.
increasing changing the chemistry from that of
As a consequence, Na24 emits electhe nuclear charge from +11 to +12,
the stable
Mg
24
Na to Mg and forming Half of any given amount of this isotope.

way
in 14.8 hours, the half-life of the
Na24
changes
in this
radioactivity. 22. In the other case,
for
ratio is too low, there are three processes

stability
which the neutron to proton which can lead to
from low states of excitation. One is alpha particle emission, which is most effective in readjusting the ratio when the stable ratio is considerably less than unity, i.e., for heavy elements. This is what one expects, because subtracting 2 neutrons and 2 protons helps the ratio most under these
conditions. It is a fact that nearly all alpha radioactivities occur in nuclei with masses of 200 or more. The alpha particle is not quite so hard to tear away as the proton because it is itself a very stable nucleus. However, alpha radioactivity
in general requires somewhat warmer nuclei than do the other kinds of radioactivity. Another and more common
course taken
by these
excited nuclei
is
the emission of a posi-
tive electron, called positron. 23. The positron has the same characteristics as the electron
its charge is positive. It does not exist at any concentration because it reacts immediately (life appreciable of about 10"4 seconds in ordinary matter) with a negative electron to turn both itself and the ordinary electron into
except that
gamma
radiation. It
is
possible to reverse this annihilation
24
299
process by sending gamma radiation through some heavy element like Pb. Sometimes, when the conditions are just
the
near the Pb nuclei help tear the negative electron being attracted gamma rays apart, to the nucleus and the positron being repelled. Figure 4 is
right, the high electrical forces
a picture of such an event taken in a Wilson cloud chamber.
The whole apparatus was placed in a magnetic field which makes electrons move in circles, the direction depending on
Fig. 4. Stereoscopic cloud chamber photographs of an electron-positron pair ejected from a 1 mm. lead foil by the gamma radiation from boron bombarded by protons. (This photograph was kindly furnished by Dr. Charles C. Lauritzen.)
the sign of the charge on the electron. Here we see one curving in one direction and the other in the opposite. They originate from the same point and obviously have practically the same
energy since the
size of the circle
positron radioactivity is the ordinary negative electron activity except that the positrons are annihilated by surrounding matter to form gamma
radiation, so we always have this gamma radiation associated with positron beta activity. 24. The third way in which a low neutron to proton ratio can be cured is by the nucleus apparently swallowing one
The
in
measures the energy. every way analogous to
of the nearest electrons, from the
first shell
of two, to convert
300
Ch.
XVI
a proton into a neutron. We do not believe ordinary electrons can exist as such in nuclei, since they are larger than nuclei, hence we think of this as a transformation not only of the proton but of the electron at the same time. This process is known as K-electron capture because the first shell of elecprobability of this hapcharge increases because the electrons are closer. An atom which has undergone K-electron capture then emits X-rays, which are readily detected. 25. Finally, we must say that the neutron to proton ratio apprently does not completely fix the properties of a nucleus of given mass. In other words, there seem to be several ways of putting a given number of protons and neutrons together
trons
is
known
as the
shell.
The
pening
incre<ises as the nuclear
to give nuclei of different properties. Such nuclei are called
isomers and afford us definite evidence of what we may call structural effects in nuclei. The more excited isomer of a pair may change to the other isomer by emission of a gamma ray or both isomers may be beta active, with different halflives, of course,
forming the same
final nucleus.
26. Table
contains facts about some of the more im-
portant radioactive nuclei, those with asterisks being found in nature and the rest having been made since the discovery
of artificial radioactivity in 1934. 27. Experimental Technique. The natural radioactive ele-
ments,
e.g.,
radium, supply us with a source of high energy
alpha particles quite useful in exciting nuclei for certain purposes. For example, neutrons are conveniently produced from beryllium metal by mixing it with radium, according to the reaction,
Be9
However,
+ He = C +
4
12
n.
in general both the energies and intensities of these sources of high energy particles are too low to allow us to study the large number of radioactive nuclei success-
radioactivity was first produced advances made in this field in the last great few years have been largely associated with the developfully,
although
artificial
this
way. The
27

TABLE
5
301
Sample
Radioactivities
ment
is
of various devices for accelerating the simpler charged particles to high energies. Perhaps the best known of these
the cyclotron, which acts by bending the

circle in
little
a a
beam into almost a strong magnetic field and giving the particles electrical push every time they pass a certain region
in the circular path. They finally become so energetic that they fly out of the circular path. Actually this occurs gradu-
ally so their
path
is like
spiral.
They then
hit the target
being studied. The other devices mainly depend on the development of very high voltages which will accelerate the particles in one push. These methods have not given energies or intensities as high as the cyclotron but they do give beams of somewhat more definite energy, which are useful for certain experiments. The neutron cannot be accelerated electrically, of course, but it is a very useful disintegration tool because it has no charge and is not repelled by the
302
Ch.
XV
nuclear charges. Most nuclei readily absorb neutrons and after having taken one are left in an excited state because
part of the neutron 's mass is converted into energy in the absorption process. The equivalence of mass and energy is a well-known law which the work in this field has verified
completely (cf. Chapter II, paragraph 3). The absorption of a neutron usually leads to negative electron radioactivity for the reasons given in the preceding section.
28. Applications. Radioactive nuclei are valuable as tracers in the study of chemical reactions. For example, it has been
even the bones
shown by feeding foods containing radiophosphorus that in the animals become radioactive in a few
days, proving that there are constant sloughing away and building up processes occurring in the live animal. There are
other important applications in the use of the radiations to destroy unwanted tissue such as cancer.
29.
The
facts discovered
about the
nuclei,
in
particular
the tremendous energies involved in their reactions, seem to supply us with a plausible explanation of the source of stellar energy. We can see that the sun, for instance, could shine for
a period millions of times longer than the age of the earth, which is approximately 3 X 10 years, if certain simple nuclear reactions were occurring. In fact, physical measurements on the sun almost require us to believe the temperature at the center to be about 10 7 degrees, at which temperatures certain nuclear reactions would undoubtedly occur. The details of stellar constitution and change certainly are not all clear but we feel that we have a good lead. 30. Finally, we must mention the determination by radioactivity of the age of rocks. The elements uranium and thorium both are composed entirely of radioactive nuclei, whose rates of decay are known accurately. The products in both cases are lead isotopes, so the amount of lead found in a rock containing a certain amount of uranium or thorium tells us how long it has been since the rock was solidified. This assumes, of course, that no lead was present when the rock formed. Examination of the isotopic constitution of
31

The
303
the lead shows whether this is true. rocks are nearly two billion years.
31.
results for the oldest
described
Nuclear Fission. The varieties of nuclear decomposition in the preceding paragraphs involve only small particles, electrons, positrons, and alpha particles, in most natural radioactive processes, and absorption of protons,
deuterons or neutrons in the artificial processes. But in January, 1939, O. Hahn and F. Strassman in Germany published their discovery that an isotope of Ba is produced by bombardment of U with neutrons. It was soon established
bombardment causes U to split into two approximately equal fragments with release of an enormous amount of energy. This process is now called "fission." Reference to Fig. 3 shows that fewer neutrons are needed in proportion to protons for lighter elements than for heavier elements, so that if one of the three isotopes of uranium, 234, 235, or 238, should split into two atoms of roughly equal weight, they would not need all the neutrons necessary to bind together 235 is the isotope the U atom. It was soon discovered that U fission and that while one neutron causes the subject to fission, probably 3 neutrons are emitted along with two
that such
fragments having prodigious kinetic energy. If the U were pure, and in a large enough mass, these neutrons could explode other atoms, setting up a chain reaction analogous to the explosion of T.N.T. but liberating vastly more energy per pound than T.N.T. The public has now been told that the bomb dropped on Hiroshima, which 235 was equivalent doubtless contained but a few pounds of U tons of T.N.T. The nature of this chain reaction to 20,000 is indicated in Fig. 5, taken from Atomic Energy by H. D.
fission
235
,
Smyth, Princeton University Press, 1945. In order to bring about such an explosion of U 235 it is 238 The composition necessary to separate this isotope from U 235 234 and 99.3% of natural uranium is a trace of U 0.7% U
,
U 238
Since
all
three are identical in chemical behavior, this
separation can be accomplished only
by taking advantage
of their slight difference in mass, in such processes as diffusion
304
Ch.
XVI
of charged
of a gaseous or a dissolved compound, or the different bending gaseous ions in a magnetic field (cf. Chapter
XII, paragraph 23). The discovery that plutonium is, like U 235 subject to fission, opened a more feasible source of atomic energy than the difficult physical separation of U 235 from U 238 Plutonium can be produced from the abundant U 238 by the following series of steps, following bombardment by slow neutrons,
,
.
6o
mm.
Np 239 2Tr> Pu 239 J.ouays

*
The
resulting plutonium, when not bombarded to produce fission, is a radioactive but long-lived element, slowly decayStray neutron
Fission
fragment
Fission
fragment
Changes
to plutonium
Fission
fragment
Fission
fragment
1
Slow neutrons
to cause
V
fissions
more
and so on
Fig. 5.
Fission of
235
.
32
305
with emission of alpha particles, and it differs enough chemically from uranium to permit separation from the latter by chemical processes, as outlined in Smyth, Chapter
ing to
U235
XVII, paragraph
produce
32.
fission.
25.
It
has been demonstrated that other
elements, for example, thorium, can be
bombarded so as to
The
release of nuclear energy at a controlled rate, for
industrial uses, instead of explosively, as with atomic
bombs,
presents interesting possibilities for providing additional power for mankind, and is therefore being actively investigated.
major obstacle to be overcome fissionable material, such as

such as
is
is
that of "breeding" from non,
U 238
more
fissionable material,
235
,
than
is
used up in the breeder.
A serious difficulty
presented also
by
producing "pile" by gerous radiation emitted in the
the necessity of surrounding the energythick, heavy shields to absorb the danfission
process.
It
is
to be
expected, therefore, that the first successful plants will be large and stationary, or for ship propulsion rather than for motor vehicles. The costs of such plants and of their fuel will
necessarily be high, hence atomic
power
will
have
difficulty in
oil
competing with power derived from water, coal, or 1 in regions remote from these latter sources.
except
Such developments would come much faster if all nations could be convinced that they have more to gain from the constructive than from the destructive uses of atomic energy,
and submit to the
rigid controls essential to safeguard all na-
tions against its devastating potentialities.

1
See further,
(a) Reference
Book
brand, Macmillan Co.,
of Inorganic Chemistry, p. 502, par. 16, York, 1952.
Latimer and Hilde-
New
edited by Glasstone, for sale by Superin(b) The Effects of Atomic Weapons, tendent of Public Documents, U. S. Government Printing Office, Washington
25,
D. C.
(c)
Annual Reports
(b).
of the Atomic Energy Commission.
Obtainable from same
sources as
(d) The Science and Engineering of Nuclear Power, Coryell and others, AddisonWesley Press, Cambridge, 1947.
CHAPTER XVII
THE PERIODIC SYSTEM OF ELEMENTS

1.
It
became evident to chemists a long time ago that
there are certain elements which
by
reason of their similarity.
may be grouped together Among such groups may be
mentioned lithium, sodium, and potassium, commonly called the alkali metals; calcium, strontium, and barium, the alkaline earth metals; fluorine, chlorine, bromine, and iodine, called
the halogens. In 1866 Newlands read a paper before the London Chemical Society in which he showed that if the then known elements were arranged in the order of increasing
atomic weight, as follows:
H
1
Li
7
Be B C
9
is
N O
F Na
19
Mg
11 12 14 16
23
Al Si P S Cl 24 27 28 31 32 35.5 39 40
KCa
a similarity between every eighth element in the that if it is divided into groups of eight and these under each other in successive rows, as follows, placed
there
series, so
H
F
Cl
Li
Be
B
Al
etc.
C
Si
N
P
O
S
Na
Mg
Ca
then the elements standing in the same vertical column are those which correspond to each other in chemical nature. It is evident from the table that this is the case. Strange as
seem, this discovery was received with some ridicule, value not appreciated till later. In 1869 this same idea was more fully elaborated independently by Mendeleeff and Lothar Meyer. Each of these chemists tabulated the elements substantially by the method shown in Table 1.
it
may
and
its
The fundamental
idea expressed
306
by such an arrangement
is
3-H
!
oo
*3|
J-t
vO
I |
2
ON
OU
CQ
Ho
U
r
"
CN
r
>a
<
.
Ô co
'^H 10
c/)
z5
(2
^
|t10
|
S*
^ <
ON 00
CQ
oo
00
S
<
*
307
308
Ch. XVII
that of the periodic recurrence of properties as the atomic
weights increase. 2. Various other representations of the Periodic System of elements have been proposed, the most useful of which,
TABLE 2
Periodic System
Li
N O 3456789
Be B
Ne
10
No Mg
11
12
Al Si P S Cl A 13 14 15 16 17 18
K Co Sc Ti V Cr Mn Fe Co Ni Cu Zn Go Ge As Se Br Kr 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
I
I
I
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te Xe 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
I
Cs Bo La *Lanthanide 55 56 57 elements
Hf Ta Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
W
6'
4
Ra Ac *Actinide 87 88 89 elements
Fr
5'
3'
4'
123
lanthanide
elements
*Actinide
elements
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71* - - Ac Th Pa U Np Pu Am Cm Bk Cf 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103
given in Table 2, is based upon the facts of atomic structure that have been set forth in the previous chapter, summarized there particularly in Table 4. The elements in the
and
several rows which are closely related are connected by lines constitute a group. The periods beginning with
PERIODIC SYSTEM OF ELEMENTS
309
K, Rb, and Cs, are longer than the preceding two periods because of the building up of the underlying levels, and there appear two elements in each row with the same number of
valence electrons. The one which more closely resembles the corresponding elements in the first two periods is connected with these by a full line and is included with them in a main
10
15
20
25
30
35
40
45
50
55
Atomic number
Ionic radii; ions with identical kernels connected by solid lines; ions Fig. 1. with identical charges, +1 and 1, connected by dotted lines; covalent radii indicated by double lines.
group, while the element which less closely resembles the corresponding lighter elements is connected with them by a broken line, indicating the smaller similarity. These elements constitute what is called a subgroup, denoted in the table by primed numbers. This arrangement of the Periodic System
should be studied, the position of the commoner elements in it learned, and the basis of its construction, as indicated by Tables 4 and 5 in the preceding chapter, thoroughly understood. 3. Almost any property of the elements or any class of
310
if
Ch. XVII
compounds,
show a
periodicity, as does the
plotted against the atomic numbers, would number of valence electrons;
however, the two most fundamental properties for an understanding of chemical and physical behavior are the size of the atom and the ease of removal of electrons. Accordingly, we have plotted, in Fig. 1, the radii of atoms in their covalent bonds, for those elements most readily forming such bonds, and also their radii as ions in solid salts, for most of the ele-
ments up to atomic number
57. In Fig. 2 are plotted the of the gaseous atoms, i.e., the work in ionizing potentials electron-volts required to detach the first electron from the
atom. Let us note particularly several facts revealed by these

figures.
4.
The
radii of the kernels corresponding to each inert
gas structure decrease regularly in each period. This accords with the increasing nuclear charge, which draws closer to
itself
of electrons
the electrons in a given energy level. When a new goup is begun, there is a jump in radius, each higher
than that of the preceding ion of the same charge. Figure 3 illustrates these relationships by showing the atoms and ions of Li, Be, Na, and Mg, drawn to relative scale. This difference also appears in comparing such structures as S +6 with three with two completed electron groups, with S
,
,
completed groups, the latter of course being much

It is interesting to
larger.
exactly
midway
note that the covalent radius of S is almost 6 between the radius of S+ and S~2 A similar
.
N, O, F, P, Cl, Br, and I. 5. The ionizing potentials of the gaseous atoms, plotted in Fig. 2, are lowest for the largest atoms, as might be expected, since the farther the negative electron is from the positive nucleus the more easily it can be removed. Except for minor fluctuations, the ionizing potential increases along each period, beginning with an alkali metal and ending with a noble gas. It should be noted that the ionizing potentials here plotted are for the first electron only. In harmony with
relation holds for the covalent radii of
the increase in size the potentials for each period are lower than the corresponding ones of the previous period.

6. Stability of Compounds. and atomic size in determining
311
The
roles of ionizing potential
chemical stability are indicated by the scheme in Chapter V, Table 7 and Fig. 8 and we may now correlate the stabilities of compounds with the
I 20
I
5
Xe
.a
I
10
Fig. 2.
20
30
Atomic number
40
60
lonization potentials of atoms.
Fig. 3.
Relation between size and structure of atoms and ions.
positions of their elements in the Periodic System. Stability is greater the lower the ionizing potential of the metallic atom and the greater the electron affinity of the nonmetallic
atom, and both become smaller as we go from the lighter to
main group. On this basis we will to be more stable than NaCl, expect, KC1 than KI, CaO than BeO, H 2 O than H 2 S. 7. Stability is also aided by small size and consequent closeness of approach of the charged atoms, a factor which
the heavier
members
of a
for example,
KC1
going
contributes to the increase in stability in going from iodides to fluorides, but which opposes the effect above noted in from LiCl to CsCl; indeed it is sufficient to reverse
312
Ch. XVII
the series in the case of the alkali fluorides, for LiF is the most stable in spite of the larger amount of energy absorbed
changing from Li to Li+. We should note, however, that the type of kernel, as well as its size, is effective in determining this attraction. A striking instance is seen in comparing LiBr with AgBr, where the distances between the charged atoms in the solid are nearly the same, although Ag+ occupies more space than Li+ in most of their compounds. We have independent evidence that Ag+ is able to distort large negative ions such as Br~, and therefore approach closer to them than would otherwise be the case. Another evidence of the superior attractive forces of ions with approximately 18 valence electrons is seen in the ability of the ions in the middle of the long periods to form complex ions. 9. The following miscellaneous examples are given as
in
8.
further illustration of the above principles. The stability of hydrogen compounds with negative elements decreases from right to left in the same period, as from HF to H 2 O to H 3 N, and from HC1 to H 2 S to H 3 P; it decreases also from the top
of a group downwards, as 2 Se to 2 Te, and from 3
HF to HI, H O through H S, H N through H P, H As to H Sb,

2
2 3
while
3 Bi is
of doubtful existence.
The
MoO3
Mods.
and
highest oxidation state of molybdenum is seen in 6 but not in a chloride, the highest being
MoF
Again, if we compare the compounds of sulfur with bromine, chlorine, oxygen, and fluorine, which is the order
corresponding to increasing electronegative character, we find that the highest bromide has the formula S 2 Br2 the highest chloride is SC1 4 the highest oxide is S0 3 but this compound breaks down rather completely above 700 C. into SO 2 and O 2 and finally the fluoride, SF 6 is an exceedingly
; ,
stable, inert substance.
Strength of Acids and Bases. If we consider a hydroxide as made up of the charged atoms, M+ O H+, we
10.
l
Chapter
See also Latimer and Hildebrand, Reference Book of Inorganic Chemistry,, III, paragraph 7.
12
313
is a possibility of dissociating, either as a base into M+ and OH", or as an acid into MO" and H+. Which of these takes place and the extent of each is dependent closely upon the relative sizes of the ions involved, although
see that there
the type of kernel is also significant. The smaller the M+ the more closely it is held to the oxygen with a consequent and H+, hence the weakening of the attraction between O
we may
and the more acidic is the compound. As illustrations note that the hydroxides of the large alkali metal ions are all strong bases, the strength increasing with the size.
less basic
The same
increase in basic strength is shown in descending group 2, but these are smaller ions and weaker bases, the weakest, Be(OH) 2 being also weakly acidic, belonging to
,
the transition hydroxides that are amphoteric. The influence of kernel type is seen in the fact that Zn+2 with an 18 electron
,
kernel, gives
11.
a weaker base,
in spite of its larger size,
than
does the smaller

are
Mg4 2
"
The more completely the electrons on the atom removed by surrounding it by oxygen atoms, i.e., the higher its oxidation number, the smaller it is and the more tightly does it hold OH" and the more readily does it allow
a stronger acid than sulfurous, SO(OH) 2 nitric acid is stronger than nitrous, arsenic than arsenous, "7 "2 etc. Again, Mn" gives an acid; gives a base while Mn" +2 a +3 an and Cr+6 an acid. Cr base, Cr amphoteric hydroxide,
,
H+ to split SO2 (OH) 2
off instead.
is
We
find, therefore,
that sulfuric acid,

;
12. The plot of ionic radii, Fig. 1, serves very well to point out the relation of acid or basic character to the position in the Periodic System. Every positive ion with a radius of less than O.S X lOr8 cm. gives an acidic hydroxide, the more
so the higher the oxidation number and the higher in the group. Ions slightly exceeding this size may give weak acids in the higher oxidation number, but the ions larger than 8 0.9 X 10~ cm. all give bases only. The region of amphoteric behavior, it will be seen, begins with Be in group 2, and runs to Al in group 3, then to group 4 and subgroup 4, with representatives from adjacent groups assisted by variations in
314
Ch. XVII
oxidation number. In group 5 we start with a 3 AsO 4 3 PO 4 strong acids, then 3 or
HNO
weak
H HPO H Sb0 4 amphoteric,

,
acid,
and hence very weak in both roles. 3 state we end with Bi(OH) 3 a weak base. In the trivalent
,
,
In group 3
we
find
B(OH) 3 a very weak

,
,
acid,
A1(OH) 3
amphoteric, and Sc(OH) 3 basic; in group 4 the weak carbonic and silicic acids, titanic hydroxide, amphoteric, zicronium hydroxide, chiefly basic, and thorium hydroxide, wholly so. 13. Similar trends are evident in the sulfides, where As2 S3 is acidic, dissolving easily in S while Sb 2 S 3 dissolves with difficulty and Bi 2 S3 not at all. The increase in oxidation number from Sb 2 S 3 to Sb 2 S 5 increases the acidic nature
,
to dissolve easily. 14. apparent exception to this trend exists in the case of the three acids of phosphorus, 3 PO 3 and 3 PO 4 3 PO 2
it
sufficiently to allow
An
which do not decrease
in strength
content. The discrepancy finds its the fact that part of the hydrogen in 3 PO 3 and 3 PO 2 is not to oxygen, but to phosphorus. Their structures linked, correspond to
with diminishing oxygen explanation, however, in
HOPOH
H
not
for the
and
HPOH
H
HP(OH) 2
,
P(OH) 3
and
former dissociates but two of its three hydrogen latter but one. 15. Oxidation State. The significance of the octet of valence electrons explains the limiting values for the oxidation states found in the various groups
atoms and the
Group
Oxidation number
012345678 1+2 + + + + +
+
3
4 + -4 _
5 3
7
1
These limiting values do not always appear in all members of a grouo. thus no other atom is able to strip 7 electrons
16
315
from a fluorine atom or 6 from an oxygen atom. The state + 8 appears only in RuO 4 OsO 4 RuF 8 and OsFg. Oxidation states lying within these extremes also appear,
,
as illustrated
by
Oxidation
no. of
Oxidation no. of Cl
P2 P2 3 H.P02
6
+5 +3 + -3
1
KC10 4 KCl0 3 KC10 2 KC10

KC1
+7 +5 +3 +1 - 1
16. Transition Elements. The horizontal relationships are rather more significant than the vertical ones among the subgroup elements. Table 3 gives the ions characteristic of
the various oxidation states of the elements from Ti to Cu.
They
all
form
also,
+2
ions
and
all
but Ni and
Cu form +3
ions.
We
see,
M++ couples, are much less so.

show an
a fairly regular trend in the potentials of the
2 e~.
The couples M++ = M+++
e~
solubility products of the sulfides almost uniform trend, as do the stabilities of the
The
complex ions, the cyanides showing maximum stability at Fe and the +2 ammonia complexes at Cu. Similar trends are discoverable in the other two transition series. Reference to Table 4, Chapter XVI, will assist in making clearer the reason for oxidation numbers lower than the
group number in the elements Sc to Cu. We see that in each series the outermost group, consisting of 4s electrons, remains at 1 or 2 while the underlying 3d group increases from 1 to
its
maximum
sum
of 10.
The maximum
and 4s
oxidation
number
is
given
by the
numbers
electrons, but smaller oxidation occur as a result of the possibility of withdrawing
of the 3d
fewer electrons. This transition from a kernel with 8 electrons

to one with 18 gives these elements the name Transition Elements. The same sort of transition occurs in the succeedto Pd where the 4d group is being filled, and ing rows from
again from
Hf
to Au, where the 5d group
is
being
filled.
t*t
O
I
*?
uu
-H
(3
000 UUU
06
X ^
L O
+ tT t
'
do
-,
I '
to
T-
oo-S
^
u
uu
10 CN (N
St^ co
^;
'
fi
+
IS
..
- 1
a,
>.
"
...
G 2
<L)
4.
"S
^ s
8
316
19
17.

The Rare
317
Earths. Beginning with Ce, atomic number 58, the 4/ group 14 begins to be filled, giving a group of elements known as the Rare Earths. These elements are
very
much
alike,
the most stable ions
18. Solubility of Salts.
The
being tripositive. solubility of salts changes in
all
all
regular order according to the Periodic System in nearly instances. This is illustrated for a single group, the second,
4.
by Table
TABLE 4
Solubilities of Salts of
Moles per
Liter at
Group 2 20
Ions,
mass divided by volume, depends, not only on atomic weight and atomic volume but on the crystal structure and coef19. Density,
which
is
in the case of solid substances,
expansion as well; hence it is not strange that the density often appears somewhat irregular. Table 5 shows and Ca which result chiefly from the irregular values for the different rates of increase of atomic weight and atomic volume.
ficient of
TABLE
Densities of Solid Elements
Group
8'
Group
10'
Fe
7.9
Ni
8.7
Ru
Os
12.0
Pd
11.5
22.5
Pt 21.4
We see, however, the general increase in density in descending a group due to the fact that atomic weight increases faster than atomic size; further, the high densities of the
elements in the subgroups as compared with the main groups

resulting from the position of the former in the troughs of the curves of atomic radii.
318
Ch. XVII
20. Tensile Strength. The metals with the greatest tensile strength are found among the subgroups, starting with 5 and extending to 10. These groups include iron and the
metals alloyed with it to make the modern alloy steels, V, Cr, Mo, W, U, Mn, and Ni. We may connect high tensile strength with small atomic volume, high melting point and
many-electron valence
21.
shells.
Elements Which Form Complex Ions. The elements most prone to form complex ions are in the subgroups and especially in the neighborhood of group I/ in the second form of the table. Complex ions with ammonia are readily given by the ions of Co, Ni, Cu, Zn, Cd, and Ag. Complex cyanides are given by the same elements, also by the platinum metals and iron. Complex chlorides are given chiefly by the and platinum metals and gold, as illustrated by PtCl 6
AuCl 4~.
22. Resemblance between the First Member of a Group and the Second Member of the Succeeding Group. Some
similarity exists between the first element in groups and 3 and the second element in the succeeding group.
1,
2,
lithium, though an alkali having a hydroxide and carbonate which are not very soluble, a rather insoluble phosphate, and a deliquescent
chloride. Beryllium is so much like elements are difficult to separate.
Thus metal, resembles magnesium in
aluminum that the two Boron is like silicon in
physical properties and gives compounds similar in many respects. The borates of all but the alkali metals, like the
corresponding silicates, are insoluble in water, and when fused tend to give glasses on cooling. 23. Radioactive Elements. As might be expected, it is the heaviest and most complex atoms which tend to break down into simpler ones, and all of the elements of higher atomic weight than bismuth are radioactive. These are, accordingly, found at the bottom of the table. The oddnumbered elements are, in general, less stable than the
even-numbered ones, as shown by their and by their life periods.
relative
abundance
25

Unknown Elements. The
319
24. Prediction of
value of the
Periodic System was demonstrated in very striking fashion by the prediction of unknown elements by Mendeleeff. At
the time he constructed his table it was obvious that several gaps should be left in order to have the succeeding elements fall into their proper groups. Such gaps were to be found at the places now filled by scandium, gallium, and germanium. From the properties of the adjacent elements, Mendeleeff predicted the properties of the unknown elements. The remarkable accuracy of these predictions is illustrated by the
following comparison of the
unknown element
called
by
Mendeleeff "ekasilicon," with germanium, discovered later by Winkler.

Ekasilicon
Germanium
At. wt. 72.5, density 5.46. Oxide GeO 2 density 4.7. Chloride 4 liquid, boiling at 86 C., density 1.887.
,
At. wt. 72, density 5.5. Oxide EsO2, density 4.7. Chloride EsCl 4 liquid,
,
boiling
1.9.
GeQ
slightly
below 100 C, density

,
Ethide,
Es(C2H 6 ) 4
liquid boiling at
Ethide,
1.
Ge(C2H5 ) 4
160 C., density 0.96.

Fluoride, EsF4, not gaseous.
160 C., density slightly

Fluoride,
liquid, boiling at less than
GeF4
white, solid.
The foregoing comparison should serve as an illustration of the value of the Periodic System to the student of chemistry, for
an undiscovered element can be foretold so brilliantly by its aid, then any knowledge a student may have of some elements may be similarly projected to deduce the
if
properties of adjacent elements.
The
use of the Periodic
the effectiveness System, therefore, enormously of a given amount of mental effort, and it is very important to form the habit of using it constantly. 25. The elements with atomic numbers greater than radon, 86, have until recently been assumed to start a row in the Periodic Table similar to the rows containing iron and the "platinum metals." Element 87 is a natural product with a half-life of only 21 minutes, but there is no doubt that chemically it is "eka-cesium," an alkali metal of group 1.
increases
320
88, gives Ra++, chemically like Ba"
1
Ch. XVII
Radium,
gives
ThO2 and
,
thorium, 90, other compounds similar to those of the

",
,
"4
group 4 elements, and uranium, 92, gives UO 4 analogous and has been generally classed as a member of to CrO 4
production at the University of California of element number 93, neptunium, designated osNp, by McMillan and Abelson, number 94, plutonium, 94 Pu, by Seaborg, McMillan, Kennedy and Wahl, curium,
group
6.
But the
artificial
9sCm, by Seaborg, James and Morgan, americium, 9sAni, by Seaborg, James and Ghiorso, has caused a reconsideration of this classification because Np does not belong to sub-group 7, with Mn, but both it and Pu are remarkably similar to U in chemical behavior, all three showing the same oxidation states, 3, 4, 5, 6, and differing only in a shift in stability towards the lower states in going towards Pu. As soon as the study of the chemical separation of these elements became a war problem of the utmost urgency, in order to separate pure Pu from the bulk of U in which it was produced
for use in the second "atomic bomb," it became evident that the additional electrons in the elements after Ra might
either go into the vacant 6d shell (cf. Chapter XVI, Table 4), which would start a series like the three "Transition Series"
paragraph 16), or they might go into the vacant 5 /shell, giving a series analogous to the Rare Earths (cf. paragraph 17), where the 4/ shell is being filled. This agrees with the fact that, like the Rare Earths, U, Np and Pu
(cf.
show the same oxidation states and differ only in their and Pu, the oxidation-reduction potentials. To separate must be so adjusted that U is in a higher state, potential 6, and Pu in a lower one, 4. It seems that the higher
states are completely missing in
aqueous solutions of
its
Am
and Cm.
The production
from uranium,
of
plutonium,
chemical separation
and use in the literally and atomic bomb, and the prospect figuratively world-shaking it opens up for the benefit of man, if he is sensible enough to use it beneficently, are such major scientific achievements
its purification
25
321
that it seems appropriate to quote a brief description of the 1 process written by Professor Glenn T. Seaborg.
"The problem of designing a process for separating plutonium was without precedent from almost every standpoint. No one had ever seen any plutonium at the time that plant design was
under consideration. The chemical properties attributed to the element at that time had been deduced solely from what might be termed secondary evidence (experiments on the tracer scale). "The novelty of the problem was enhanced by the fact that not only was Pu 239 to be the first artificially produced isotope to be seen but as an element it fell beyond the confines of the classical periodic system. These curious conditions, in themselves, would not necessarily produce serious obstacles WTC they not coupled with other aspects of the problem of an unconventional nature for
scale operation. Both the plutonium and the fission products from which it was to be separated would be present in extremely small concentrations in the uranium. These separations
industrial
would require specialized techniques. The formidable feature of the undertaking was, however, that these minute amounts of the fission product elements would in turn have to be separated from the plutonium to the extent that only of the order of one part per million of each would remain. To add to the complications, the separations process would have to be carried out entirely by remote
control because of the staggering levels of gamma-ray activity associated with the fission products. As a result, it was imperative that the process be adaptable to simple equipment that would
require a minimum of maintenance and that the limits of control be not too stringent.
4
'Although four types of method for chemical separation were

volatility, adsorption, solvent extraction,
examined
tion
and
precipita-
precipitation process. S. G. Thompson is largely responsible for the conception and early development of the process actually used. The process depends on the coprecipitation of the plutonium along with a carrier
finally
the
process
chosen
was a
precipitate, a procedure which has been commonly used in radiochemistry. One of the most interesting and awe-inspiring aspects
in the
development of
this process
was the necessity
of the process at a time

l
when only microgram amounts
for the testing of cyclotron-
Chemical and Engineering News, 23, 2190 (1945).
322
It
Ch. XVII
produced plutonium were available.
was necessary to
test the
process at concentrations corresponding to the full level of Hanford plant operation and therefore the experiments had to be conducted
on the ultramicrochemical scale of operation, which employed volumes of only micro-liters. This involved a scale-up between these experiments and the final Hanford plant by a factor of about
surely the greatest scale-up factor ever attempted. In spite of these difficulties, the chemical separation process at Hanford was successful from the beginning and its performance exceeded
10 10
,
expectations. High yields and decontamination factors (separation from fission product activity) were achieved in the very beginning and have continued to improve with time.
all
"The
of
precipitation process which is being used involves the use an alternation between the IV and VI oxidation states of plu-
tonium, as pointed out in the Smyth Report. The process involves a precipitation of plutonium (IV), with a chemical compound as a carrier, then dissolution of the precipitate, oxidation of the
plutonium to the VI state, and precipitation of the carrier compound while the plutonium (VI) remains in solution. Fission products which are not carried remain in solution when Pu (IV) is precipitated, and fission products which carry are removed from
the plutonium when it is in the VI state. Successive oxidationreduction cycles are carried out until the desired decontamination is achieved.
"These statements on the Hanford Separations Process, to be a gross oversimplification of the actual process. There are carried out in all some thirty major chemical reactions involving hundreds of operations before the plutonium emerges from the process. The plants themselves defy description with their massive structures and their intricate maze of equipment, piping, and remotely operated controls. The preliminary design
sure, represent
was underway at a time when the world supply of naked eye. This remarkable program of investigation with microscopic and sub-microscopic quantities marks only one of a large number of amazing and so far unheralded
of these plants
plutonium was
invisible to the
achievements of the
men
of chemistry
who developed
the chemical
separation processes which were used on the Atomic

It is
Bomb Project."
now
appropriate to consider the relation of both the
rare earths
and the trans-uranium elements to the Period
CO O
W
r^
'
*o
00 CO
CJ
S
(J
O
!S
<
i c
O
JC.
&g'
03
OH
^H ON
O ON
CQ
oo 00
r^
-H
o
*C
Oj
iis
oJ
<O
O-C/5
323
3 "1 ^ 2 <o
*a
324
Oi. XVII
System, as set forth in Tables 1 and 2, where the rare earths were "unclassified." The reason for this was, of course, that the rare earths, like the elements in the neighborhood of iron, have no prototypes among the lighter elements. However, the parallelism between the rare earths and these new
elements does lend significance to their proper classification in the Periodic System. Table 6 gives the row containing the trans-uranium elements arranged in parallel with the first part of the row containing the rare earths, together with
oxidation states which they exhibit. It is noteworthy that the most stable oxidation state rises uniformly till uranium is reached, then falls stepwise, reaching 3 only with americium
and curium. In the rare earth series there is a similar rise and fall but it is less pronounced and has its maximum not in the element above uranium but in praseodymium, consequently there is little chemical resemblance between the several elements 59 to 62 and the ones directly below them, 91 to 94. It is ordinarily more helpful to correlate uranium with tungsten and molybdenum than with neodymium. Nevertheless, the evidence seems unmistakable that, as explained above, the two rows are similar in that /-electrons are being added instead of ^-electrons. Seaborg has called
the
new
series the "actinide series,"
because
it
starts with
actinium, just as the rare earths, starting with lanthanum, may be called the "lantjianide series." It is interesting to note that he chose the name americium as a parallel to eu-
ropium, and curium, in honor of the Curies, who discovered radium, as a parallel to gadolinium, after Gadolin, who discovered several of the rare earths. Berkelium (pronounced "berk-Hum") and Californium were
produced in 1950 by Seaborg and his coworkers, Ghiorso and Thompson. Berkelium has a half-life of 4.6 hours, californium
of only 45 minutes, hence their detection
the
in
among the products of bombardment was a chemical tour de force, particularly the case of californium. It was based upon the parallelism
that had been established as existing between the rare earth series and the lanthanide series which permitted a prediction
25
325
as to just when the californium should appear in the elution of the cations adsorbed in a column of a certain resin. It ap-
peared in the exact drop expected and was identified by its radiation. It is clear that so evanescent an element could not have been found by a merely random search. This was another
major triumph
for the Periodic
System
in the
hands of men
who knew how
to use
it.
Exercises
1. In what regions of the Periodic System will elements be found which have the following characteristics most strongly marked: tendency to form stable compounds with hydrogen, tendency to form ammonia complex ions, tendency to form strongest oxygen acids, radioactivity, maximum positKe oxidation number, lowest melting point, minimum negative oxidation number, the strongest reducing power, amphoteric nature of the hydroxides,
the greatest tensile strength? 2. Arrange the following elements in their proper order in groups 1 and 2 of the Periodic System: Li, Mg, Ba, Ca, K, Na, Cs, Be, Rb.
3. BaCl 2 is moderately soluble, CaCl 2 is deliquescent; what can you conclude regarding RaCl 2 ? How would you expect the solubilities of LiCl and NaCl to compare? 4. How do each of the following properties vary from left to
right in the same row of the Periodic System (a) the basic character of the hydroxide, (b) the melting point, (c) the positive oxidation number, (d) the electrical resistance of the element?
:
5.
and
their
Discuss the trend of properties of the elements of group 2 compounds as you descend the group.
6. Compare the saltlike characters of binary compounds with the positions of their constituents in the Periodic System.
7.
From
the place of
its
Cd
in the Periodic
(a)
System, what deduction
would you make regarding:

(b)
the solubility of
8.
the melting point of the metal; sulfate; (c) the ionization of its chloride?
,
Compare the strength as acids of (a) H 3AsO 3 and H 3SbO 3 (b) HsAsOs and HsAsO^ Justify your answers by either experimental facts known to you, or by theoretical considerations, or by
valid analogies.
9.
How
with the places of Al and
do the differences between HsAlO 3 and B in the Periodic System?
H BO
8
agree
326
10.
NaNO2
or
Ch. XVII
Explain on theoretical grounds which you would expect
to be more hydrolyzed, (a)
NaAsO 2
(b)
Na 2SO 3
or
Na TeO
2
Name the halogens in their order, (b) Which one has the greatest tendency to take on electrons? (c) Which has the highest melting point? (d) Which is the weakest oxidizing agent? 12. From the position of beryllium in the Periodic System, deduce (a) whether Be(OH) 2 or Mg(OH) 2 is the stronger base; 2S; (c) whether BeSC>4, (&) whether BeS could be precipitated with or MgSO 4 is more soluble (d) whether Be or evolves more heat upon reaction with chlorine.
11.
(a)
Mg
13. Explain on a theoretical basis which of the 2 elements, Ti or Th, would (a) more likely form a compound with hydrogen; (b) be the better conductor of electricity; (c) be more easily reduced from its dioxide; (d) give the more basic hydroxide; (e) give a more
completely hydrolyzable chloride.

14. Classify the following
compounds according
to the oxidation
number
(d)
0")
3
H P0
of the phosphorus they contain: (a)

2
;
P 2O 5
2
;
(b)
PC1 3
4
(c)
(*)
PH
(e)
H
.
P2
(/)
HPO
(g)
NaPO
(h)
PbHPO
PC1 5
Ca(H 2 P0 4 ) 2
15.
Deduce from
Os or Ir should show the higher oxidation number, (b) Rh ++ or Pd + + should give the more stable complex with NH 3 (c) Ni(OH) 2 or Co(OH) 2 should be the stronger base.
(a)
;
their positions in the Periodic
System whether
16.
Compare the
5
stabilities of the trichlorides of the
elements
in
group
and
in
justify
your comparison upon

7.
theoretical grounds.
17. State 5
chemical or physical characteristics of the element
below iodine
18. (a)
"
1
group
Which would you expect " Fe 4 or Co++ (b) H 2 S or

;
to be the stronger reducing agent,
H Te?
2
Explain your answer very

agent,
briefly.
of Ni and Co (a) whether Ni"4 or Co+ is the stronger reducing agent; (b) whether Ni(OH) 2 or Co(OH) 2 is more easily soluble in NH 4OH; (c) which element is harder (d) which has the higher melting point (e) whether CoS or NiS is more soluble in water. 21. From your knowledge of the properties of Fe++ and Cu ++ compare (a) the solubility of NiS and CuS, (b) the stability of the
""1"
~*~
;
19. Which would you expect to be the stronger oxidizing Ni(OH) 2 or Fe(OH) 2 ? Give the basis for your answer. 20. Deduce from the positions in the Periodic System

ammonia complexes of Ni+ + and Cu" Fe(OH) 3 and Ni(OH) t
.
327
"
1
4
",
(c)
the oxidizing power of
*22. On the basis of your knowledge of atomic structure, offer an explanation for the fact that the formula for mercurous ion is Hg 2++ rather than Hg+.
23.
The atoms X, Y, and Z have atomic weights
that order.
Y has
2, 8, 8, 1
electrons outside
its
increasing in nucleus. The atomic
number
of
is
15 less
greater (than
X) by
26.
than that of Y, while Z's atomic number is From your knowledge of the Periodic
Table identify X, Y, and Z. Which is the strongest reducing agent? Which has the greatest tendency to form complex ions?
24.
Compare
the basic properties of the hydroxides of sodium,

briefly in
magnesium, and aluminum, and explain very the atomic structure of these elements.
25.
20,
terms of
The elements A, B, C, D, E have atomic numbers 11, 1, 18, and 17 respectively, (a) Which are metals? (b) What compounds does E form with the others? (Use the symbols above in writing
formulas of compounds.) (c) If the atomic weight of many neutrons are in its nucleus?
26.
is 41,
how
Compare Cu and
(c) (e)
as to (a) atomic radius, (b) ionizing
potential,
structure of outer electrons of the
ion, (d) electric
heat conductivity, (/) melting point, (g) density, (K) atomic number, (i) strength as reducing agents, (j) tendency to form complex ions.
conductivity,
*Question of greater
difficulty.
CHAPTER
XVIII
ORGANIC CHEMISTRY
understanding of molecular structure was first obtained in connection with the compounds of carbon. Both plants and animals are made up chiefly of carbon compounds, from which it is evident that nature has prepared an enormous variety of them. It used to be thought that such compounds could be synthesized only through the aid of living matter,
1.
An
whence they were called organic compounds. Although we have since learned that no such limitation exists, we still designate the chemistry of the carbon compounds as organic chemistry, and find it advantageous, on account of its peculito treat it as a very distinct branch of chemistry. labors of chemists have added greatly to the number of carbon compounds until today there are known over
arities,
The
200,000 of them. The majority contain only carbon, hydrogen, oxygen, and nitrogen. Now the simple determination of the number of atoms of each kind in the molecule does not suffice to identify the substance, or to suggest methods for
preparation, any more than given amounts of lumber, nails, bricks, mortar, etc., would serve to identify a house. Indeed there are many instances where several substances contain atoms of the same kind and number. For example,
its
two substances having the formula C2 6 O: one ordinary alcohol, a liquid with a boiling point of 78 C. and a density of 0.789 at 20 C.; the other is dimethyl ether, 23.6 C. under 1 atmosa gas which becomes liquid at phere pressure, and which has a different odor and generally different properties. Taking a more complex formula such as C 6 Hi 2 O 6 we find a much larger number of corresponding substances, in this case not less than 64. Such substances are called isomers. The differences in their properties can,
there are
is
,
328
ORGANIC CHEMISTRY
329
of course, be
this
due only to differences in arrangement of the atoms within the several molecules. The determination of
arrangement has therefore been a fundamental task in the study of carbon compounds. 2. The nature of the evidence used in the determination of the structure of these molecules is not difficult to compreis four.
used is that the covalence of carbon ever necessary to assume that any carbon atom is surrounded by more than four other atoms. Thus we may start with CH 4 which is known as methane
hend.
first principle
if
The
It is rarely
a prominent constituent of natural gas, and in which we might be inclined to say that the carbon is negative, and we can change progressively, by the successive substitution of chlorine for hydrogen, to CH 3 C1, CH2 C12 CHC13 which is chloroform, and finally CC1 4 (used in fire extinguishers and in cleaning). In this last we would doubtless conclude that the carbon is positive, but in the intermediate compounds we see that the question of sign
is
,
,
or marsh gas, and
becomes rather confusing. Since we usually consider hydrogen positive and chlorine negative, we might assume the charges in CH 2 C1 2 and +2 in 2 in CH 3 C1, on the carbon to be CHC1 3 that is, different in all five cases. However, we note
,
that in
all of
them the carbon remains attached
to four other
atoms, without regard to sign. The organic chemist takes as fundamental the existence of four 'bonds" for every carbon atom. Each bond is usually indicated by a simple dash, thus the four compounds given
'
above are usually written as
follows:
H
i
H
i
H
r
I
H
i
Cl
i
H-C-H H-C-C1 H-C-C1 Cl H H

I
C1-C-C1
I
C1-C--C1.
I
Cl
Trichlorom ethane or chloroform
Cl
Tetrachloromethane or
Methane
Monochloromethane
Dichloro-
methane
carbon
tet-
rachloride
a 'bivalent" element is combined with carbon it is assumed that two of the bonds of carbon are required, thus forming a
If
'
330
Ch. XVIII
"double bond/' in harmony with the fact that a carbon atom can hold but two atoms of oxygen, as shown by the following formulas:
H
I
H-C=O
Formaldehyde
0=C=O.
Carbon dioxide
Other examples of formulas written upon this basis will be found later in this chapter. 3. The Electron-Pair or Covalent Bond. The reason for the four bonds per carbon atom is seen in the four valence electrons, each forming a pair with an unpaired electron from another atom. The hydrogen atom, .H, and the chlorine
atom,
.
Cl
:,
alike
have one such electron and can form not only

:
Cl
and
Cl
Cl
Cl:
but the intermediate compounds as well. An oxygen atom, O, can take up 2 of the electrons of a carbon atom, leaving the other two free to unite, say, with hydrogen, giving
H
H :C:: O
:
which would be written ordinarily with a "double bond" between C and O, thus,
H-C=0.
Such bonds may,
bonding electrons
those in
in
it
is
true,
CHU
are
be more or less polar; the almost equally shared but
CCU
are shifted towards the chlorine.
4. Arrangement of Atoms about the Carbon Atom. If the atoms about the carbon atom in such a compound as Ct^Cb were all in the same plane, there would be a possibility of two arrangements which might give rise to isomers having somewhat different properties, as follows:
ORGANIC CHEMISTRY
331
H
H-C-C1
I
Cl
H-C-H.
I
Cl
Cl
In one case the like atoms are adjacent, in the other they are opposite. The fact is, however, that neither in this case, nor yet when any other atoms or groups have been substituted for the hydrogen and chlorine respectively, has it been possible to prepare
different isomers.
However, if the surrounding atoms or radicals are arranged in tetrahedral form about the central atom, as shown in Fig. 1, there can be only one arrangement, for each corner of J
.
Fig. 1.
Tetrahedral arabout a car-
a tetrahedron
, .
on atom.
is
The
adjacent to every other. non-existence of such isomers, therefore,

is
evidence for
the tetrahedral arrangement.
This tetrahedral arrangement again corresponds to the nature of the isomers found in cases where the central carbon
Fig. 2.
Optical isomerism.
atom is surrounded by four different atoms or groups. Figure 2 shows two arrangements which are different in the sense that the right and left hands are different, or right- and lefthanded screws are different. In each case, one is the mirror image of the other. These are called asymmetric forms. There
332
exist great
numbers
just
Ch. XVIII
of such isomers, alike in all ordinary
and left-handed screws may be properties, identical in weight, form, etc., but which show a remarkable difference in optical behavior. Light which is made to vibrate
as right-
one plane, or polarized, when passing through one of these isomers will be rotated to the right, and through the other an equal amount to the left, just as right- and lefthanded screws would be rotated equally in opposite directions in advancing a given distance. This behavior is thus consistent with the tetrahedral structure. We have, therefore, very good evidence that the atoms about a carbon atom are arranged approximately in tetrahedral manner. The representation of this upon paper is not very satisfactory since it requires the use of perspective, but since optical isomers are possible only when the four
all in
surrounding atoms or groups are different, it suffices for most compounds to use the plane arrangement. 5. Paraffin Series. The immense number of carbon compounds is chiefly due to the ability of carbon atoms to link to each other indefinitely. The simple linear arrangement
of the carbon
atoms gives
rise
to the paraffin series of
The following structural formulas show the first few members of the series. This type of molecule can evidently be extended indefinitely, for the substance C 60 Hi 2 2 has been prepared. The series can obviously be represented by the general formula C n H 2 r>+2
hydrocarbons.
H
I
H-C-H
I
H
Methane
II H-C-C-H II
H H
Ethane
H H
H H H III H-C-C-C-H III H H H
H-C-C-C-C-H
HHHH fill
HHHH
I I I I
HHHHH
I
'Propane
H-C-C-C-C-C-H.
HHHHH
I I
I I
Butane
Pentane
ORGANIC CHEMISTRY
characteristics of the series are indicated in Table
333
The
1,
containing selected members. Its members are constituents of paraffin petroleums and the neighboring members come
over together as the petroleum is distilled. The gaseous members are contained in natural gas, the low boiling liquids are in gasoline, and as the boiling points rise we find the substances successively in "distillate," kerosene, "light" and "heavy" lubricating oils. When the melting points
enter the range of ordinary temperatures
we
get vaseline,
then soft paraffin, and then hard paraffin. Beginning with butane, isomers are possible. Thus we may have, in addition to the straight chain, an arrangement with a side chain, as follows, called isobutane.
H
I
H-C-H
H
I I
H
I
I
H-C-C-C-H.
H H H
This has somewhat different properties, e.g., a boiling point 17 C., whereas normal butane boils at + 1 C. With of
pentane there are two additional isomers, and the number rapidly increases with increasing molecular complexity. 6. To justify these structures we must introduce a second principle used in determining molecular constitution of carbon compounds. This asserts that in organic reactions ordinarily the smallest possible number of bonds are broken. Organic reactions are characterized by a much greater slowness than
reactions. It is often necessary to heat the substances together for hours. This inertness makes reacting it possible to disturb only a part of the molecule, so that a certain group, or "radical," known to be present in the molecule before the reaction, is likely to remain intact in
most inorganic
some product
of the reaction.
334
7.
Let us
illustrate this principle.
Ch. XVIII
the structure already assigned, in By allowing bromine to act upon ethane in the presence of
TABLE
Paraffin Series of
i
Ethane can have only view of the covalences.
Hydrocarbons
hydrogen by bromine and to + Br2 = C 2 H 5 Br + HBr. prepare This can hardly have any other than the ethane structure,
light it is possible to replace
monobromoethane, C 2 H 6
H H
I I
H-C-C-Br.
I
I
H H
(Remember that
all
of the carbon
bonds are
alike, in
view
of their tetrahedral arrangement, so that the formula just written is identical with the following, which only appears to
be different because they are written in one plane.)
ORGANIC CHEMISTRY H H
I
335
H-C-C-H.
t
I
Br
Now if this bromide is treated with zinc, we get zinc bromide and butane, the isomer boiling at + 1 C. It seems that the bromine has been removed and the remainders of the two molecules have joined together without further alteration.
(This remainder, C 2 H is called the ethyl radical.) To consider this isomer as isobutane would obviously require us to assume
r) ,
much more complicated and hence far more improbable breaking and rejoining of bonds. Isobutane must be prepared in a very different way. 8. As a further example of the application of this principle to the determination of structure, let us consider the isomers first mentioned, ethyl alcohol and dimethyl ether, both C 2 HeO. Starting with the methane structure, we will consider CH 3 to be the methyl radical, which would be left by the
that the reaction involved a
removal of one atom of hydrogen. Methyl iodide (or monoiodomethane) when treated with a solution of gives methyl hydroxide (methyl alcohol, "wood alcohol"),
KOH
H
I
H-C-O-H.
I
H
(Additional evidence for this structure will be given later.) Treatment with sodium replaces one hydrogen atom, giving
H
I
H-C-O-Na.
I
H
If this is
48
allowed to react with methyl iodide, sodium iodide produced, and the simplest possible way for the remainders
336
2
Ch. XVIII
of the 2 molecules to react
an oxygen atom linking
is simply to join together, with methyl groups.
H
I
H
I
H
|
H
| I
H~C-O-!Na + li-C-H H H
"
' I I
= Nal+
H-C-O-C-H.
I
is the gaseous isomer, and is called dimethyl oxide, or dimethyl ether. The structure of the other isomer is indicated by the fact that it is easily derived from ethyl bromide by the action of a solution of KOH.
This
II H-C-C-Br + KOH II
H H
H H
H H
-
H-C-OOH + KBr.
H H
II II
This isomer, therefore, appears to be ethyl hydroxide in structure. To assume that this reaction involves breaking the bond between the carbon atoms to give dimethyl ether would appear highly improbable, just as it would be to assume that the previous reaction would directly link the carbon atoms. It is usually possible to prepare a given compound from more than one source, or to decompose it in more than one way. Where the same structural formula can account for all known reactions it naturally inspires a high degree of confidence. There are, however, cases where extensive rearrangements evidently take place during certain reactions. The determination of structure in such cases has often proven
very difficult, and the history of organic chemistry is not without its sharp controversies. 9. Unsaturated Hydrocarbons. There are a number of hydrocarbons which contain less than the maximum amount of hydrogen. Thus ethane is C 2 H 6 while ethylene is C 2 H 4 The unused carbon bonds are commonly supposed to be
,
10
ORGANIC CHEMISTRY
337
joined together, thus
H
\
H
/
C=C
/
\
giving a double bond. This corresponds to a bond of 4 electrons instead of 2, and may be represented
H H
Two
double-bonded molecule are
H H H H
C::C
other possible configurations of the electrons of a
H H
:
C C
:
and
C C
:
ii
ii
ii
both of which represent high-energy or "excited" states of the molecule. The molecule spends but a small portion of the time therein. The double bond is more or less readily "broken" by the addition of other atoms giving "saturated" compounds. Ethylene may be made to add more hydrogen, becoming
ethane.
10. Still
C2 H 2
more hydrogen may be lacking, giving acetylene, usually prepared by the action of water on calcium
carbide,
CaC 2
The
and
+2H
= C 2 H2
Ca(OH) 2
acetylene molecule requires the asumption of a triple bond, if the quadrivalence of carbon is to be maintained,
is
written
Hydrocarbons with longer chains
may have
double or
338
bonds occurring anywhere
3 2,
Ch.
XVIM
triple
in the chain,
2
2
such as
H C-CH=CH
in
and
HC^C-CH -CH
A
--C^CH.
11. Derivatives of the Paraffin Series.
hydrogen atom
may be replaced by another atom or radical giving different series of derived substances. The nomenclature of most of these is based upon the name of the univalent radical that would be left upon the hypothetical
a paraffin hydrocarbon
removal of an atom of hydrogen. The first eight of these radicals are as follows: CH 3 - methyl; C 2 H 5 - ethyl ;C 3 H 7 - butyl; C 6 H U - amyl; C 6 H 13 - hexyl; C 7 H 15 propyl; C 4 H 9 octyl. It will be seen that the names of all heptyl; C 8 Hi 7 but the fifth are derived from those of the corresponding might be called pentyl, hydrocarbons. The radical CsHu but is called amyl instead. The name of the derivative is thus simply derived in most cases from that of the radical: for example, C 2 H 6 C1 is ethyl
chloride;
C 4H9 I
is
butyl iodide;
CH 3 O CH 3
is
dimethyl
is
oxide, or, since such oxides are called ethers, dimethyl ether;
C 2 H5-O-C 3 H 7
nitrate.
is
ethyl-propyl ether;
will
C 2 H 5 NO3
ethyl
Other examples
appear in the following para-
graphs.
Chlorine and bromine react with the hydrocarbons, replacing one or more directly hydrogen atoms. Iodine is substituted by way of other HI = CH 3 I H 2 0. A derivatives, for example, CH 3 OH few examples of such derivatives have already been given. Other structures can be written ad libitum from the principles already given. Isomerism is encountered even in such a simple derivative as C 2 H 4 Br2 which can be either
12.
Halogen Derivatives.
H H II H-C-C-H
H H
or
II
H-C-C-Bi.
Br Br
II II
Br
is
The
first is
got
by adding bromine
to ethylene, and
there-
14
fore
called
ORGANIC CHEMISTRY
339
ethylene bromide, while the second is called ethylidene bromide. (Both are dibromoethanes.) 13. Alcohols. The hydroxides of the paraffin radicals are
the alcohols. In fact, the
name
alcohol has caused the radicals
of the paraffin series to be called the alkyl radicals. If we represent such a radical by the symbol, Alk, we can express
The
the general formula of an alcohol by the formula, AlkOH. first member of the series is 3 OH, called methyl alcohol
CH
or methanol. (This latter name is preferable, because it avoids the suggestion of beverage use, which is very dangerous.) It is one product of the destructive distillation of wood,
hence the name "wood alcohol." The second member is C2 H 5 OH, ethyl alcohol or ethanol. This is the alcohol chiefly produced in fermentation. The
as the important constituent of various beverages, which he regards as a blessing or a curse, according to his point of view, but he rarely realizes that it
layman usually thinks
of
it
plays an exceedingly important part in chemical industry. 14. We may introduce in this connection a third principle
in determining molecular constitution, which is that substances which have similar constitution show similar behavior. Water may be regarded as hydrogen hydroxide, and
which aids
this corresponds to the similarity of certain of their reactions, for example,
methyl alcohol as methyl hydroxide, and
HOH + Na = HONa + |H2 CH OH + Na = CH ONa + \ H2

,
HOH + 3 CH OH +
3
3
PBr3 = PBr3 =
3
3
HBr + H 3 PO3 CH 3 Br + H3 PO3

,
Again, the alcohols act similarly to bases in some of reactions, as shown by the equations
thei<?
NaOH + HC1 = H 2 O + NaCl, CH3 OH + HC1 = H2 O + CH3 C1,
340
f
Ch. XYlir
NaOH + H 2 SO4 = H2 O + NaHSO 4 H 2 S0 4 = H 2 + CH 8 HSO 4

,
2 2
CuOH = Cu 2
)
+H
2 O,
CH 3 OH = (CH 3 2O + H 2O.
graphic formulas of the alcohols should, therefore, be related to those of water and bases in being hydroxides.
The
H
I
H-O-H
Na-O-H
H-C-O-H.
I
H
Alcohols are divided into three classes, according to the of carbon atoms linked to the one bearing the hyThe three structures are: droxyl.
number
The vacant bonds may be occupied by

further carbon atoms. There
either hydrogen or are also alcohols containing
more than one hydroxyl. and glycerol or glycerin.
We
will
mention only two,
glycol,
H
I
H
I
H-C-O-H
I
H-C-O-H H-C-O-H H
I
H-C-O-H
I
H-C-O-H.
I
H
Glycerol
Glycol
17
15. Ethers.
ORGANIC CHEMISTRY
When
is
341
alcohols are distilled with sulfuric acid
removed and alkyl oxides, called ethers, are produced, as illustrated by the preceding reaction. The most important is diethyl ether, used extensively as an anaesthetic. The general formula of an ether is Alk O Alk. The two alkyl
water
groups need not be the same. 16. Ketones. The primary, secondary, and tertiary alcohols behave differently upon oxidation. The tertiary are split
up into simpler products. The secondary are changed to ketones, whose general formula is
Alk- C- Alk.
II
O
Thus secondary propyl
alcohol,
CH
I
H-C-OH
I
CH
would give dimethyl ketone,
CH
I
I
c=o
CH
commonly
17.
3
called acetone, a liquid
much used
as a solvent
for varnishes, etc.
Aldehydes. The primary alcohols upon mild oxidation give first aldehydes, characterized by the group
-C-H.
The
2 CO, formaldehyde, made by simplest aldehyde is air and vapors of methyl alcohol over a glowing passing platinum catalyst. It is a gas, soluble in water or alcohol,
342
is
Ch. XVIII
and
much used
as a disinfectant.
The second
is
acetalde-
hyde,
H
I
H-C-C-H.
I
II
H O
The next would have ethyl in place of methyl, and so on. 18. Acids. The further oxidation of the aldehyde group
gives the carboxyl group,
-C-O-H,
II
often written
-COOH,
O
characteristic of organic acids. becomes acetic acid,
Ethyl alcohol thus
finally
H
I
H-C-C-0-H, H O
I
II
in the process of
series
forming vinegar. The acids of the paraffin many important substances. The following are the names corresponding to the number of carbon atoms
include
present: 1, formic; 2, acetic; 3, propionic; 4, butyric (the acid responsible for the odor of rancid butter); 4, valeric;
16, palmitic; 18, stearic. We may mention also oleic acid, which differs from stearic in having a double bond between two of its carbon atoms. The sodiujn .salts of these last three
acids are present in ordinary soaps. There are other acids containing
more than one carboxyl
group, such as
O=C-OH O=C-OH
I
O=C-O-H H-C-H O=C-O-H

I
0=C-0-H H-C-H
I
I
H-C-H
I
O=C-O-H.
Succinic
Oxalic
add
Malonic add
add
19
ORGANIC CHEMISTRY
343
There are others containing both carboxyl and hydroxyl groups, such as tartaric acid, one of the acids of grapes, and citric acid, the acid of lemons and oranges.
O=C-O-H
I
H-C-O-H H-C-O-H O=C-O-H

I I
H C-COOH
2
I
H-O-C-COOH
I
H C-COOH.
2
Tartaric acid
Citric acid
The two middle carbon atoms
of tartaric acid are joined each to four different atoms or groups, so that optical isomers are possible. The construction of tetrahedral models is neces-
sary to make this altogether clear. Citric acid has no asymmetric carbon atom. 19. Esters. We have seen that the alcohols are hydroxides, analogous to bases, and that they react with acids (slowly)
with elimination of water (which is usually removed by mixing with sulfuric acid) to form substances analogous to
salts; these are called esters.
have already given examples inorganic or organic acids. of the former. The latter may be illustrated as follows:
We may We
3
have esters of either
C H OH +
2
5
H-O-C-CH
II
->
CH
2
-0-C-CH + H O.
3
2
II
o
Ethyl alcohol
Acetic acid
o
Ethyl acetate
The
esters of the organic acids are pleasant smelling liquids,
many
of
which are used
in artificial flavorings.
Glycerol forms important esters. Its trinitrate is commonly called nitroglycerin, which is a constituent of dynamite and of smokeless powders. Its esters with the higher paraffin
acids are the fats. Glyceryl tripalmitate is palmitin, the chief constituent of palm oil; glyceryl tristearate is stearin, the chief constituent of beef tallow; glyceryl trioleate is olein, found in olive oil, lard, etc. Most fats and oils of animal or
vegetable origin contain varying amounts of these esters.
34*
20.
alkyl radicals gives amines.
Ch. XVIII
Amines. The substitution of the hydrogen atoms of
ammonia by
H
I
H
I
H
I
CH,
I
N-H H
I
N-CH H
I
N-CH
I
N-CH,.
I
CH
CH
A
Ammonia
Methylamine primary amine
Dimethylamine A secondary amine
Trimethylamine
tertiary
amine
The amines obey the rule regarding the parallelism of properties and structure in that they are chemically like
ammonia.
NH 2 and COOH in the same of amino acid. These are peculiar in having molecule gives an both a basic and an acidic group; hence both are weak, and there is the possibility of self-neutralization. These acids can combine with each other indefinitely to form the proteins, essential constituents of our food, and the basic material
21.
The combination
of living organisms.
of the preceding compounds we have straight or branching chains of carbon atoms. There is another important class of organic compounds in which
22. Cyclic
all
Compounds. In
called cyclic or aromatic
the carbon atoms are joined to form closed rings. They are compounds, to distinguish them from the straight chain or aliphatic compounds.
C6H 6
The most important aromatic compound

,
in
is benzene, which the carbon atoms form a ring with a hydrogen
atom on
each,
H
C
H
C
HC( )CH
TJP nv^ v \
(
I
'
'
HC
or
II
X
I
r*tr v^rl
ur*
rlLxv \
c
<a)
&
H
Armstrong and Beyer
H
(6)
KekulS
23
ORGANIC CHEMISTRY
345
23. Resonance in the Benzene Molecule. What to do about the fourth carbon bond has always been something of a problem, for the organic chemist does not like to abandon
the quadrivalence of carbon; in spite of the extraordinary stability of benzene. Indeed, the extra bond can be called into play, strong reduction adding six more hydrogen atoms.
Kekule drew alternating double and single bonds, as shown at (&), but benzene does not show the ordinary reactions of the double bond, such as the addition of bromine. If the
carbon bonds are represented in tetrahedral form, it is possible to construct a very compact structure corresponding
to the
It
first
formula.
seems probable that the extra electrons or bonds in the benzene molecule are not permanently in any one position, such as those represented by the above two formulas, but are moving about with great rapidity from one extreme Kekule formula to the other, with the double bonds in the alternate positions, with the Armstrong and Beyer position traversed on the way. There is reason to believe that still another position is involved, represented by
H
C
/
I
HC
II
CH
II
HC
\ I/
CH.
H
In representing the benzene ring for ordinary purposes usually ignore the above complexities and write a simple hexagon, with hydrogen understood at the corners unless occupied by some other element or radical.
we
Evidence for the ring structure is found, first, in the fact that when one hydrogen atom is substituted by something else, say bromine, giving monobromobenzene, there are no
346
Ch. XVIII
if bromine is substituted in the such as hexane, three isomers corresponding open are possible, depending upon whether the bromine is on the end carbon, next to the end, or the third from the end.
isomers.
On
the other hand,

chain,
Additional evidence
tution
is
furnished
by the number
of disubsti-
products. There are three dibromobenzenes, cor-
responding to the three following arrangements:
Br
Pr [J
Ortho-
,JBr
Meta-
Which
of the three substances actually corresponds to each arrangement is readily determined by substituting a third
hydrogen atom, when the orthodibromobenzene can give two isomeric tribromobeiazenes, the meta three and the
para only one.
Benzene Derivatives. If we designate the benzene ring minus one of its hydrogen atoms as the phenyl radical by the symbol 0, then we can represent very simply a few
24,
of the important derivatives as follows:
<t>
<t>
<
OH COOH CH3
Phenol (carbolic acid) Benzoic acid Toluene

Aniline
<
NH2
NO2 CH 2 OH CHO CO CH 3 N=N
<f>
<
Nitrobenzene
<t>
<t>
Benzyl alcohol Benzaldehyde
<
<t>
Phenyl methyl ketone Azobenzene
<
Diphenyl
25
ORGANIC CHEMISTRY
may
be made, as in
347
Further substitutions
OH
NH
BrAB,
NO,
Paranitrophenol
U
Br
Tribromaniline
A AOH V COOH V
3
CH
COOH
Metatoluic acid
Orthohydroxybenzoic
acid (Salicylic acid)
The
artificial
dyestuffs are rather complicated molecules,

rings.
most of which contain one or more benzene

the simplest
is
One
of
indigo,
CO
/
\^
CO
\
C.
\
C,
eH 4
\
(_x
eH 4.
NH
rings linked together, illustrated
NH
by the
following:
There are other substances containing several benzene
Naphthalene
Anthracene
25. Polymers. Many natural organic materials owe their usefulness to their mechanical strength or their elasticity, and to the fact that they do not dissolve easily in the ordinary
which are likely to come in contact. Wood, cotton, wool, silk, and rubber are familiar examples. These properties arise from continuous linking of atoms, usually in chains in which certain groups are repeated over and over again, whence they are called polymers. Natural rubber consists of indefinitely long chains in which the repeated group is
liquids
_OC = C-CH CH
3
H H
The
single carbon-carbon
bonds are tetrahedrally arranged,
348
The
Ch. XVIII
so that the
stretched.
fiber, is
atoms form a zigzag chain which can be bent or repeated group in cellulose, wood and cotton
H H
I
O O
I
H-C-C-H
-c
/ /\
2
\
I
c-oH
H-00
/I
H C-0-H
It is possible to polymerize artificially certain simple molecules to produce polymers having often very useful properties. Probably the simplest type of polymerization occurs with molecules having double bonds on the carbon
atoms at each end
of the chain.
These bonds can be opened
up by the aid of suitable reagents or catalysts, furnishing electrons for forming single bonds to link together the end
carbon atoms of the different building units. An exceedingly simple case is presented by the formation of "koroseal," a
rubberlike polymer.
tion:
The
following are the steps in the forma-
H H
'
H H
Pt
'
'
H H
NsOH
'
'
'
c=c
-2J-
ci-c-c-ci
-2+
c=c
H H
Ethylene
II
H H
Ethylene chloride
II
II
Cl
Vinyl chloride
HHHHHHHH
I
I I I
etc.-C-C-C-C-C-C-C-C-etc.
I I I I I
I
Cl
Cl
Cl
Cl
"Koroseal"
25
ORGANIC CHEMISTRY
result is
oils, for
349
The
and
an artificial rubber, inert to oxidizing agents which there are many uses.
A similar process yields "neoprene."
H H
I I
H
HCl
I I I I
H
I
H-OC-H
Acetylene
>
C=C-C=C -^>C=C-C=C
I
Cl
H H
Chloroprene
H
I
H
I
etc.
C C=C C
I I I I
etc.
H
The repeated
windows
Cl
H H
Neoprene
unit in "plexiglass," or "lucite," used for

is
of airplanes
H CH
I I
-C-CI I
H C=O
I
O-CH
The
unit of "nylon," a
now well-known,
valuable substitute
for silk is
OHHHHO
II
I I I I I!
HHHHHHH
I I I
-C-C-C-C-C-C-N-C-C-C-C-C-C-N-
HHHH
I
HHHHHHH
I I I I
I
different molecules are linked together to form the repeating unit in both "butyl rubber" and "buna-S" or
Two
"styrene" rubber, as follows:
350
Ch. XVIII
H
I
I
H IIICH c=c-c=c +c=c

I
I
H
I
H
I
H H CH
-c-c=c-c-c-cI
I I
III
I I
H H H H
Butadiene
H CH
H H H H H CH
Butyl rubber
laobutylene
H
I
H H H
Butadiene
+ C=CH
-c-c=c-c-c-cI
I
III
I
H H H
Stryene
H/\H
Styrene rubber
The above
are only illustrations selected from a long
list
of polymers that have achieved great commercial prominence 1 during recent years.
26. Silicones.
2
An
interesting
and useful
series of
com-
pounds has recently come into prominence in which silicon atoms are involved in place of carbon. Metallic magnesium reacts with a mixture of an organic chloride, RC1 and SiCl 4
to yield compounds of the type R m SiCl n where which can undergo further changes, as follows:
,
m+
n =
4,
R
RSiCU
RSi(OH) 3
I
-Si-O-Si-OI
HjO
R*SiCl 2
Si(OH) 2
-Si-OI
R
HjO
RsSiCl
R,SiOH
R,Si-0-SiR 3
References: P. O. Powers, "Synthetic Resins and Synthetic Rubbers," Chemical and Engineering News, Vol. 20, p. 536 (1942). H. L. Fisher, "Synthetic Rubbers," Ibid., Vol. 21, p. 781 (1943). 2 Reference, Shailer L. Bass et a/., "Silicones High Polymeric Substances,"
26
ORGANIC CHEMISTRY
first
351
The
two types
are repeating units in polymers, the
third type gives liquids with low freezing points, low vapor pressures, low rates of change of viscosity with temperature,
remarkable chemical stability. Greases have been prepared which do not melt between - 40 C. and 200 C. A plastic material has been produced which can be moulded with the fingers, like putty, but will bounce like rubber when thrown onto the floor.
Exercises
1.
Write formulas of the following so as to show the constituent

Propyl alcohol,
(&)
radicals.
(a)
(d)
(/)
Methyl-ethyl ether,
(c)
Dibutyl ketone,
Amyl
An
acetate, (e) An aldehyde containing acid containing six carbon atoms, (g)
two carbon atoms, Hexyl chloride, (h)
Ethyl nitrate, (i) Diphenyl ketone, (j) Pentadecane, (k) Dijnethyl sulfate, (/) Ethyl sulfide, (m) Dipropyl oxalate, (n) Methyl amine. (0) Propyl oyanide, (p) Dichloromethane, (q) Trichloromethane, (r) Glyceryl triacetate, (s) Phenyl amine, (/) Acetic anhydride.
(h) a hydrocarbon with ten carbon atoms and twenty-two hydrogens, () CH 3 COOH, (j) C 2 H 6 OH, (*) C B H 6 COOH (cyclic), (I) HCHO,
4
Name the following compounds: (c) C 8 H (a) C H Br, (6) CH 3 -CO-CH (/) C H -O-C 2 H (e) CHiCOOCsHu,
2.
3
7
3,
17
NH
5,
(g)
2 (d) C H 6 C H (OH)
,
(cyclic),
2,
(m)
3.
C 2H 4
Give the principles used organic compounds.

4.
in
determining the structure of
What
evidence
is
there that the benzene molecule has a ring
structure ?
5.
Define:
isomer,
organic
chemistry,
all
aromatic
compound,
aliphatic
6.
compound, unsaturated compound.

the structural formulas for
Show
the isomers of mono-
bromobutane (C 4 H 9 Br).
7. Certain organic compounds have the property of rotating the plane of polarization of polarized light which passes through
them.
(a)
What
property of the molecule
is
responsible for this effect?
Modern Plastics, Vol. 22, pp. 124-126, 212, 214 (November, 1944). E. G. Rochow, "The Organosilicon Polymers," Chemical and Engineering News, Vol. 23,
p. 612 (1945).
352
(b)
Ch. XVItf
Give the structural formula of a molecule which has
this
property.
8.
Three isomeric dichlorobenzenes, CeH^CU, have the following

melting points,
is
When
52.9. 17.6, (c) the benzene ring, the first gives 3 different trichlorobenzenes, the second gives two, and the third gives one. Identify the dichlorobenzenes as ortha, meta,
different
(a)
24.8,
an additional Cl
substituted for
H in
(b)
and para
9.
respectively.
10.
How many dichloro-propanes are there? How many isomeric monochloro-monobromo-propanes

How many
are
there?
*11.
optical isomers are possible with monochloro,
monobromo ethane?
*12. "Mustard gas" vapor is toxic in a concentration of about 0.02 milligram per cubic meter. What is its partial pressure at that concentration in millimeters of mercury? Its formula is C 4 H8C1 2 S.
*Questions of greater difficulty.
CHAPTER XIX
DISPERSED SYSTEMS
I a distinction was made between heteroand homogeneous material, between mechanical geneous mixtures and solutions. It was there pointed out, however,
1.
In Chapter
that, while such distinctions as this are often useful, there
may
be no sharp line of demarcation. We here deliberately examine the intermediate zone. If we have a bottle containing water in the lower portion and moist air in the upper, we would not hesitate to call the system heterogeneous. Even if the water were* blown into the air from an atomizer, we would doubtless still consider the system heterogeneous. Suppose, however, that we could break up the droplets into successively smaller and smaller ones, ending finally with molecules of
water vapor in air. The system finally resulting we would have to consider as homogeneous. At what stage in the disintegration process, we may well ask, did the system cease to be
heterogeneous and become homogeneous? We might imagine a similar gradation starting with sand and water, which would be heterogeneous, through successively finer and finer suspensions of silica powder in water until we would have a solution of silica molecules in water. There is, evidently, no sharp boundary between systems certainly heterogeneous, on the one hand, and solutions, on the other hand, and between these two extremes there are systems which should have some of the characteristics of both. These we will call dispersed systems, one phase being highly dispersed in another. The following scheme gives a survey of the types of dispersed systems, classified according to the nature of the phases. We distinguish, on the one hand, between the dispersed phase, which is discontinuous, minute isolated
353
354
particles,
Ch.
XIX
drops or bubbles, and the dispersing the other hand, which is continuous.
Dispersed phase
Inclosing
medium, on
phase
Type
Liquid
Gas
Liquid
Fog
Gas
Solid
Foam
Smoke
Solid
Gas
Solid
Gas
Liquid
Solid
foam
Liquid Liquid
Solid
pumice) Emulsion
(e.g.,
Suspension
Liquid
Solid
Solid
Many
alloys
In addition there are systems, such as sponge, charcoal,
and gelatin jelly where both phases are continuous, with a network structure. The most important of these from a chemical stand point are emulsions and suspensions, and our attention will be
largely confined to them.
Brownian Movement. As the dispersed phase in suspensions and emulsions becomes more and more finely divided it is possible to get systems in which the two phases do not separate on standing under the influence of gravity. A rela2.
tively large
will fall
its size,
body like a grain of sand, dropped into water, through the water at a rate of speed dependent on the difference in density between it and water, and
the viscosity of the water.

fall
very small sand particle will more slowly through the water, because as the size
diminishes, the surface, upon which the resistance depends, does not decrease as fast as the weight. Fine suspensions, therefore, settle out more slowly than coarse ones. When
a'sufficiently
it
may
be seen that
minute particle is observed with a microscope it no longer falls in a straight line, but
follows
an irregular zigzag path. follows: the molecules of water,
The
reason for this
is
as
according to the kinetic
theory, are In rapid motion, with a mean kinetic energy proportional to the absolute temperature. In disordered motion of this sort some molecules, at a given instant, will
DISPERSED SYSTEMS
355
be moving more rapidly and some more slowly than the average. When the particle of sand is so large compared with the water molecules that it is being bombarded by a
very large number of the latter, the effect of differences in their kinetic energy will be neutralized but when the particle an especially hard impact on one is sufficiently minute, side of it may not be neutralized by the impacts of other molecules on the other side, hence the particle will be slightly displaced. Since these abnormally hard impacts are constantly
;
I
Rote of fettling-
M
Rapid
Nil
Very rapid
Nil
Slow
Small
Nil
Brownian movement
Fig. 1.
Rapid
Effect of size
on
particle sedimentation.
occurring irregularly from different directions the result is the irregular zigzag movement of the particle above referred to. As smaller and smaller particles are taken, the chances
for inequality in the momentum of the impacts upon them increase, and their resulting displacement also increases, for
a molecule of water striking a small body will have more effect on it than upon a larger one. In fact it can be seen by
the aid of the microscope that the particles of fine suspension are in much more violent motion than those of a coarse
suspension. This progression
is
illustrated in
Fig.
1.
This
movement
is
known from
its
discoverer as the
Brownian
movement, and gives us very

of the kinetic theory.
3.
direct evidence of the truth
When
sufficiently fine particles are taken, the
Brownian
movement overcomes the effect of gravity so that the particles remain in permanent suspension. The system is then known
as a colloidal suspension, or colloidal solution. There will be,
356
Ch.
XIX
in such a suspension, if time is allowed, an increasing concentration of particles from the upper to the lower portions of the vessel, analogous to the increasing concentration of the atmosphere from high altitudes to lower. In fact, a French
physical chemist, Perrin, showed that the rate of increase in the concentration of the particles in suspensions obeys the same laws that govern the change in barometric pressure
with altitude, a most striking proof of the truth of the kinetic theory and of the real existence of molecules. 4. The dividing line between suspensions which settle out on standing and colloidal suspensions, which remain permanently suspended, is purely one of convenience, for by
applying centrifugal force it is possible to separate suspensions that would not do so under the influence of gravity alone. In general, colloidal suspensions cannot be separated
by
filtration
through ordinary
filters.
5.
It is possible to distinguish in practice
between true
colloidal solutions or suspensions by aid of the great differences in their rates of diffusion. The Brownian
solutions
and
movement movement
of colloidal particles of the
is
so
much
less
than the
much
smaller molecules of substances in
true solution that the former diffuse from regions of greater to regions of smaller concentration with much less rapidity.
The first distinction between the two types of solutions was made upon this basis by Graham, in 1862. He obtained
the following figures for the time required diffusion of various substances:
for the equal
HC1 NaCl
Sugar
MgS04
Albumin Caramel
2.3
49 98
To
the
name
the class of substances which diffuse slowly he gave colloids, from the Greek name for glue, a member
of this class.
6. The molecular weight can be calculated from the rate of diffusion and also from the lowering in vapor pressure or in freezing point, as explained in Chapter IV. These methods
DISPERSED SYSTEMS
357
show that molecular weights may cover the entire range from ordinary large molecules to suspended particles, with no natural dividing line between homogeneous and heterogeneous solutions. The following approximate values are illustrative.
Cane sugar
Quinine citrate Milk albumin
Pepsin
7.
342
1357
17,500
Insulin
41,000
44,000
20,000,000
Egg albumin
Tobacco mosaic virus
35,500
is
When a viewed by transmitted light it usually appears homogeneous, like a true solution, its color depending on the size of the particles and on the nature of the
Optical Properties of Colloidal Suspensions.
colloidal suspension
material.
By
reflected light
different color
we usually notice a somewhat and an opaque, muddy appearance similar
to that of ordinary suspensions. The microscope will detect particles as small as 0.000,25 millimeter in diameter. Smaller
particles tfian this cannot be
viewed directly as they are
smaller than the
wave
length of light, so that the latter
cannot be regularly reflected from them. It is possible, however, to detect the presence of particles as small as 0.000,006
millimeter
by looking
at
them
in
a strong transverse beam
of light against a dark background. (The diameters of the molecules of most ordinary substances are less than 0.000,001
millimeter.) Although no real image of the particle may be seen, there is a scattering of the light by it so that a bright speck of light can be seen in the microscope. The same effect
is
responsible for the visibility of a
beam
of light in a dark
room through illumination
of dust particles, invisible, pereven in a microscope. microscope arranged for use haps,
with a powerful transverse illumination against a dark background is called an ultramicroscope. By knowing the concentration of the material in a colloidal suspension, and counting the number of particles in a tiny beam of known dimensions it is possible to determine the average size of the particles. 8. Adsorption. Solid surfaces have the power of condensing gases upon them. The amount of gas so adsorbed depends
358
Ch.
XIX
upon the nature and area of the surface, the temperature and the nature of the gas. The lower the temperature the more slowly do the gaseous molecules move, and the more
easily are they held by the attraction exerted by the solid surface. Hence the gases which are most easily condensed to the liquid state are also more highly adsorbed by solid
all gases helium, which boils at 4.5 K, is least followed by hydrogen, whose boiling point is 20.5 K, adsorbed,
surfaces.
Of
then by gases like nitrogen, oxygen, etc., then by ammonia, water vapor, etc. It is a fact familiar to chemical analysts that considerable amounts of water may be condensed upon the surfaces of pieces of apparatus like crucibles and glass beakers, so that it is necessary to have them in a dry atmosphere in order to get exact and reproducible weights. If
the solid
surface
is
is
porous, like charcoal, or finely powdered, its vastly increased, allowing the same amount to
adsorb very much more of the gas. The use of charcoal to adsorb odorous gases in this way is very familiar. 9. A similar adsorption of dissolved substances can take place from solutions upon solid surfaces immersed in them. "Boneblack," formed by the strong heating of ground bone, turning its animal matter into charcoal, is used in the refining
of sugar to remove the yellow coloring matter present. The colored bodies are mainly substances with large molecules,
which are readily adsorbed on the large surface of the boneblack, from which the solution of sugar can be filtered clear and colorless. Cottonseed oil is decolorized by fuller's earth in the same way. On account of the large surface exposed by even a small amount of solid in colloidal suspension (a cube having a diameter of 1 cm. and a surface of 6 cm. 2 if divided into cubes with a diameter of 0.0001 cm., would have a surface of 60,000 cm. 2 ) the adsorption of dissolved substances upon the colloidal particles exerts an important
,
effect
upon
their properties.
Migration of Colloidal Particles. An especially important effect upon the properties of fine suspensions is exerted by adsorbed ions. It is seldom that electrolytes
10. Electrical
11
DISPERSED SYSTEMS
359
is
are absent from aqueous suspensions, and even where such the case, the ions of water may be differentially adsorbed.
ions in excess,
Certain kinds of suspensions are prone to adsorb positive whereby the particles acquire a positive charge,
while others, in a similar way, become negative. As a result they are able to migrate with an electric current flowing through the solution, the direction depending upon the sign
of the adsorbed ions. This
phoresis.
phenomenon is known as cataThe speed with which they move is comparable

OH~
OH"
FeXOH
mFe 2 O 3
4-
O O
H H
Fig. 2.
Relation between chemical nature and particle charge.
to that of the slower ions, about 7 mm. per hour under a drop of potential through the solution of 1 volt per centimeter.
thus possible to classify suspensions as positive or negative, just as the ions themselves were classified in Chapter VIII. Among the positive suspensions are those of the metallic
It
is
hydroxides and sulfides; the negative suspensions include arsenous sulfide, silicic acid, graphite, and the noble metals.
Figure 2 illustrates how the positive charge on ferric hydroxide results from its basic nature, while the negative charge on silicic acid corresponds to its acid character. There is no essential difference between adsorption of OH" and adsorption of water followed by ionization of H+.
11. Relation between Charge and Stability. Coagulation. Even though a suspended particle may be so small that its Browniani movement prevents its settling out under the
influence of gravity, a suspension of such particles
may
not
360
Ch.
XIX
be stable, because of the tendency of the particles to adhere

to one another on impact, forming successively larger aggregates until settling out can occur. This process may be
seen
when
silver chloride is
is
formed by mixing
if
its ions.
At
first a very fine suspension formed, which, centrated, appears quite stable, and may run through an
not too con-
ordinary filter. On standing, however, and more rapidly if the solution is heated and stirred, these extremely fine particles adhere to each other, forming eventually the familiar curdy precipitate of silver chloride. Now the effect of electrolytes upon the stability of such a suspension is very great. The
presence of a charge upon the particles tends to make them repel each other and to prevent coagulation, so that a small amount of the proper electrolyte increases the stability.
Suppose that we are dealing with a negative colloid, like As2 S3 If some electrolyte is added whose positive ion tends to be highly adsorbed, it may partly displace the ion giving the negative charge, leaving the particle neutral and free to coagulate with others like it. 12. Hydrogen and hydroxide ions are usually highly
.
adsorbed, so that the addition of a small amount of aci(\ to a suspension of arsenous sulfide suffices to coagulate it, while the addition of a small amount of alkali to a positive suspension like that of ferric hydroxide coagulates it com*
pletely. In general, then, negative suspensions are coagulated
by acids and positive suspensions by alkalis. There appear to be no striking differences in the extent to which most other ions are adsorbed, but the effect of the charge of the adsorbed ion upon its ability to coagulate a suspension is
very great. Let us suppose that Na+, Ca++, and A1+++ are adsorbed by suspended As2 S3 to the same degree. It is evidently not the amount of substance adsorbed but the amount of positive charge that it carries with it that determines its ability to neutralize the charge on a negative suspension. To have the same amount of electricity adsorbed, we will need but half as much of the doubly charged Ca"^, and but one third as much of the triolv charged A1+++. as we will of
16
DISPERSED SYSTEMS
"
361
the singly charged Na+. Hence it will take very much less Ca^4 and still less A1+++ to have the same effect as a given amount of Na+. Moreover, it is the amount adsorbed, and not the amount in solution, that determines the coagulating effect, and since the concentration of a substance in solution
more rapidly than the amount adsorbed, the concentration of Na+ in the solution must be considerably more than three times that of the A1+++ in order that the amount
increases
of the former adsorbed be three times the latter. 13. Aluminum sulfate is extensively used in connection with filtration plants to increase the efficiency of the filtration on account of the great coagulating power of aluminum ion upon the negative suspension of mud in water. The
aluminum hydroxide formed by the hydrolysis
of the alumi-
a positive colloid, and also aids considerin the coagulation, since a positive colloid acts like a ably positive ion in neutralizing the charge on a negative suspension. 14. The ions in sea water have a similar coagulating effect
sulfate
is itself
num
upon muddy
15.
river water discharged into
it,
a factor which
aids in the formation of bars at river mouths.
are very fine suspensions, which are themadsorbed or absorbed in animal or vegetable fibers. selves When the fiber is unable to hold the dye permanently, the color may frequently be made "fast" by using a coagulant, called a "mordant." The mordant is the salt of an ion with a multiple charge like AI+++ or Sn^4"*-, which can diffuse into the fiber and hydrolyze, giving a positive hydroxide, which can hold the dye firmly. A "lake" is a pigment made of such a coagulum of a hydroxide, like A1(OH) 3 with a suitable dye. The "purple of Cassius" is a similar coagulum of gold and stannic hydroxide, formed simultaneously in the reaction of stannous ion with chloroaurate ion, as follows:
,
Most dyes
AuCl 4
3 Sn++
12
2
HO Au +
2
Sn(OH) 4
12
H+
+ 8 CP.
washing precipitates it is often found that the and run through the precipitate tends to become suspended
16. In
362
Ch. XIX
filter. It is possible to prevent this resuspension by washing with water containing a little acid, or ammonium salt, or ammonia, etc., as the case requires. 17. The effect of the charge of negative ions in coagulating positive suspensions follows the principles laid down for
corresponding effect upon negative colloids. Ferric hydroxide suspension, for example, is more easily coagulated by sodium sulfate than by sodium chloride. 18. Emulsions. We have thus far been considering dispersed systems in which a solid is suspended in a liquid. We will now consider those systems, called emulsions, in which the suspended phase is a liquid. Much of what has been said in
the
regard to solid suspensions applies here. When the suspended droplets are small enough, as in cream, they are subject to Brownian movement, though in this case not sufficient to
the top by reason of gravity. The optical properties of emulsions are similar to those of suspensions. It is possible, however, to have stable emulsions
prevent their slow
rise to
with the suspended material less highly dispersed and in larger amounts than is the case ordinarily with solid suspensions, as illustrated by cream and mayonnaise dressing. In order to do this, however, an emulsifying agent must be
used, for
The
two pure liquids will not form a stable emulsion* reason for this is as follows
:
suspended droplets come together they will tend to coalesce into one, for the surface tension operates to make the surface as small as possible, and one spherical drop will have less surface than two of the same total volume.
In order to prevent their coalescing it is desirable to have the liquid in which they are suspended viscous, but especially is it necessary that the film of liquid which separates them
When two
when they
like the
are close together should be difficult to rupture, soap film which prevents two adjacent air bubbles from coalescing. Now a stable liquid film can be produced by some substance which greatly lowers the surface tension of the liquid. An exact proof of this could be given, but the
following simpler explanation
may
suffice.
The diminution
19
DISPERSED SYSTEMS
363
in the surface tension is an evidence that the substance added diminishes the attractive forces of the molecules within the liquid; consequently there will be a tendency for molecules of the solvent to restore the condition of the pure solvent,
where the molecules are probably closer together, by squeezing out, as it were, the molecules of the solute, which will
therefore tend to be concentrated at the surface, still further lowering the surface tension. In fact we find that the surface
tension of soap solutions is much less than that of water, and also that the tension at a surface that has stood for a short
time
is less
than
it is
at a fresh surface, as illustrated
by the
following figures:
Surfacati-Tension
Fresh surface
Old surface
Water
1.25 per cent soap solution
79 62
79 26
19.
Suppose, now, that

3,
we consider a film
of such a solution,
representing in Fig.
at a, the greater concentration of
the soap at the surface by the shading. If a strain is put upon the film so that it starts to rupture at a certain place, repre-
Fig. 3.
Automatic strengthening
6,
of a film of soap solution
on
stretching.
to bring from the interior to the surface at this point solution in which the soap is at first less concentrated, and whose surface tension is, therefore,
sented at
the effect
is
greater
than that of the old surface. Consequently, whenever rupture threatens, the film becomes automatically stronger, and hence is stable. Sufficient soap dissolved in water will therefore give either a stable foam, if shaken with air, or a stable emulsion if shaken with oil. Other substances, like
saponin, gelatin, albumen, the casein of milk, etc., may have the same effect in greater or less degree. The substances
in the
egg act in this
way
in
making mayonnaise. Milk, when
364
Ch.
XIX
concentrated in the form of evaporated milk, can serve also

for
It is possible to
oil
making mayonnaise. have
either phase the inclosed phase, the
being the inclosing phase in mayonnaise that ated/' and in the water-petroleum emulsions give trouble in oil refining. 20. It follows from the foregoing theory that emulsion favored will be the one in which the
has 'separthat often

the type of
emulsifying
'
agent
is
soluble in the outer
phase, the one in which stable films are desired. Thus, sodium
soaps favor oil-in-water emulsions, while aluminum soaps favor water-in-oil. There is a tendency, also, for the phase present in smallest amount to be the inclosed
phase, and one of the secrets of success in making mayon-
accordingly to wet the sides of the vessel with egg, and to add the oil slowly
naise
is
at
first.
Further assistance is given Preferential wetting. Fig. 4. by using a vessel whose material is better wet by the outer phase, e.g., glass or china rather than metal.
21. Differential Wetting.
The
different degrees of wetting
between liquids and solids is often quite evident. Everyone is familiar with the fact that tiny globules of mercury roll about on a wood surface that water globules are only partly flattened out on a paraffin surface while they spread completely on clean glass. The difference between a clean and a greasy windshield is well known to all automobile drivers. The simple experiment illustrated in Fig. 4 shows the tendency of water to displace chloroform on a glass surface while chloroform displaces water on a bright metal surface. Ac;
21
DISPERSED SYSTEMS
365
cordingly, if metallic powder were dropped onto the interface between these liquids, it would descend into the chloroform
while glass powder would be floated on the interface, supported by the surface tension. If one liquid does not completely displace the other, but the interface forms some finite
may remain in the interfacial but protruding more into one liquid than into the other. If the less-wetting liquid is in drops, the adhering
angle of contact, the particles
surface,
Fig. 5.
Toluene emulsified
in
water by powdered pyrite.
particles will then be mostly on the outside of the drop, and can serve as a sort of armor to hold drops apart and prevent coalescence. Solid powders may thus serve as emulsifying agents, the type of emulsion being determined by relative wetting as just explained. Figure 5 illustrates an emulsion
of toluene in water
which
is
by the aid of powdered pyrite, FeS 2 wet somewhat better by water than by toluene.
The
particles of pyrite can be seen coating the droplets, 6 shows sticking to them but mainly in the water. Figure
the water as the inside phase in kerosene, brought about by using powdered charcoal, wet better by kerosene than by
water.
Particles of metallic sulfide ores can be effectively purified
from accompanying earthy material by grinding the crude ore with a suitable oil and water, suspending the mass in
366
Ch.
XIX
water to which a foaming agent has been added and blowing air bubbles up through the suspension. The oil-coated metallic particles trying to escape from the water, attach themselves to the bubbles and are carried out over the rim of the tank where the froth is broken down and the pure ore recovered; the water-wet earthy impurities remain in the tank. This process is known as ore-flotation and has greatly increased
the efficiency of ore-recovery.
Fig. 6.
Water
emulsified in kerosene
by powdered
charcoal.
22. Lyophilic Colloids. There are a number of colloids, most of which are obtained directly or indirectly from plant or animal organisms, which readily remain in combination
with water or some other appropriate solvent. These include albumens, soaps, gums, tannins, starch, gelatin, glue, caramel, rubber, and nitro-cotton (nitro-cotton is extensively used in making collodion, celluloid, smokeless powders, varnishes, and artificial leather). These substances instead of being
bring into solution and easy to coagulate, like suspensions, give solutions or jellies very Where water is the dispersing liquid, as with albumin rapidly. or gelatin, the colloid may be called hydrophilic, signifying " that it is a "lover of water, and in distinction to the hydrodifficult to
most
colloidal
24
DISPERSED SYSTEMS
36?
phobic colloids such as arsenous sulfide. Where some other dispersing medium than water is used the more general terms lyophilic and lyophobic may be used, signifying respectively "lover" and "hater" of the solvent. Thus nitro-cotton is lyophilic to a mixture of ether and alcohol but lyophobic
towards water. These colloids have also been called "reversible colloids/' because, like gelatin, they can usually be easily redissolved after drying out. Again they have been called "emulsion colloids" since they behave in many respects like emulsions.
It seems rather certain, however, that in many cases the dispersed phase is not in the form of droplets, but consists rather of threads which stretch through the solution forming
a network. Such solutions, even when very dilute, often have a very high viscosity, and when more concentrated
yield a jelly. Ions
may
migrate through a gelatin
jelly
almost
as rapidly as through water. 23. Some of these substances, such as gelatin and albumins, are made up of amphoteric molecules containing both carboxyl
and amino groups. These can unite with each other indefinitely
to give the large colloidal aggregates or the solid jelly structure. The addition of either acid or alkali tends to break up the aggregates, decreasing viscosity and making the solution
more
difficult to gelatinize. If
treatment with acid or alkali
it
the jelly does not melt upon at least swells by taking up
more water. Since most
of the material of
it
which living organisms are

will
made
is
colloidal in nature,
be perceived that the
subject of colloids
biologist.
becomes one of great importance to the

If
24. Protective
Colloids.
an
with a metallic suspension, the oil the metal particles, and the resulting system would behave essentially like a pure emulsion. Similarly, when a "reversible" colloid, or hydrophilic colloid, is mixed with a hydrophobia colloid, the mixture behaves like a colloid of the former class.
Since the hydrophilic colloids are relatively stable, a hydro-
emulsion were mixed drops would tend to inclose

oil
368
Ch.
XIX
phobic colloid
if
may
be
made
stable in this way. For example,

is is
present in a solution in which silver chloride formed from its ions, each particle of the silver chloride
gelatin
is
coated with gelatin so as to prevent the coagulation that would otherwise ensue. The retention of this highly dispersed
state in the solidified gelatin
makes
is
possible the photographic
dry plate. Again, when gelatin

arsenous sulfide
to coagulate
it.
it
added to a suspension of requires much more concentrated acid
25. Preparation of Colloidal Solutions. In addition to the colloids obtained from biological sources, such as gelatin,
starches, etc., it is possible to prepare highly dispersed systems of other materials by various methods, which may be classified as dispersion or condensation methods,
albumins,
according, respectively, as we start with undispersed material or with molecularly dispersed material, molecules and ions.
(a) Dispersion Methods. Colloidal solutions of the nobler metals may be prepared by passing an arc between electrodes of that metal under water. The metal is vaporized in the arc and the vapor is condensed to solid particles in a highly
dispersed state.
Previously coagulated material may often be redispersed by washing out the coagulant, as occurs in washing certain precipitates. Basic ferric acetate, precipitated by boiling
a solution containing ferric acetate, may be redispersed by washing with water containing a trace of acid. Some substances can be dispersed by the aid of a "peptizer," usually a protective colloid, taking its name from the action of pepsin in dispersing albuminous material in the process of digestion. Thus graphite can be peptized, or suspended, by grinding it with tannin. The resulting solution is known commercially as "aquadag," and can be used as a lubricant. The cleansing action of soap, which is in the colloidal state when dissolved in water (not when in alcohol),
is
of this nature.
(6)
Condensation Methods.
it is
solution
By starting with ordinary possible to get suspensions by suitable means.
25
DISPERSED SYSTEMS
ferric chloride
369
Thus a solution of a H+, OP, and Fe(OH) 3

is
always contains free
(or basic chloride), the last of

it
which
not pass through a very fine membrane like parchment. Accordingly, if such a solution is separated by parchment from pure water, the H+ and CP can diffuse out. The Fe(OH) 3 accumulates as the hydrolysis proceeds, as represented by the equation,
will
partly agglomerated, so that
Fe+++
+ 3 OP + 3 H
= Fe(OH) 3
+ 3 H+ +
CP.
By
continually renewing the water into which the hydro-
chloric acid diffuses, the hydrolysis may be made complete, leaving a colloidal solution of ferric hydroxide. Such a process
differential diffusion is called dialysis* Other be obtained in colloidal solution by the same hydroxides can method. That a colloidal solution is obtained by dialysis but not by the addition of alkali, is due to the coagulating effect of the hydroxide ion which would be present under the latter
of separation
by
circumstances.
Whenever a relatively insoluble substance can be produced in the absence of any considerable amount of electrolytes, it
is
possible to prepare
it
as a colloid.
will give
Thus
the action of
,
H
A
2 S on a solution of As2 O 3
a suspension of As2 S 3
since the substances involved are all practically un-ionized. 2S suspension of HgS can be obtained by the action of
on Hg(CN) 2 for the same reason. Colloidal gold can be prepared by the reduction of a very dilute solution of HAuCl 4 by some nonionized reducing agent, such as formaldehyde,
CH 2 O,
some
or a solution of phosphorus in ether. The addition of protective colloid, like gelatin, allows the solution of
the metal to be prepared in much more stable form, and also more concentrated. The "argyrol," used in treating cold in the head, is a concentrated protected solution of
colloidal silver.
370
Exercises
1.
Ch.
XIX
Discuss the conditions necessary for the existence of stable
foams and emulsions.

2.
Summarize the
characteristics of hydrophilic
and hydro-
phobic colloids, respectively.

3.
Assuming that you have discovered that a
certain colloid
migrates with the positive current, decide whether it would be coagulated more easily by HC1 or NaOH. 4. When a substance is dispersed in a liquid the behavior of
the system will depend mainly upon the following factors: (a) the (b) the magnitude of the surface tension between the phases, (c) whether the dispersed phase is solid or liquid, (d) whether the dispersed particles absorb positive or negative ions more readily. Decide what effect, if any, each of the above factors would have upon each of the following phenomena: (1) the Brownian movement, (2) the electric migration, (3) the
size of the dispersed particles,
absorbing power,
5.
rate of diffu$ion T (4) coagulation, (5) separation on standing, (6) (7) protective action on other dispersed substances.
What
conditions should be observed in the formation of
colloidal solutions?
effective
Outline experiments to enable you to determine the most means for coagulating a colloidal suspension of an unfamiliar substance.
6.
7. Make a classification of dispersed systems that will, in your opinion, best express their various behaviors.
8.
How
would you expect the Brownian movement to be
affected by (a) the size of the dispersed particles; (b) the viscosity of the dispersing liquid; (c) the temperature; (d) the concentration
of suspended particles?
9.
pensions;
State essential differences between (a) emulsions and sus(b) suspensions and colloidal suspensions; (c) hydrophilic
colloids.
and hydrophobic
10. Classify
the following into two groups,

(a)
hydrophilic and
hydrophobic, respectively:
gelatin;
(/)
albumen;
graphite;
(d)
(i)
As 2 S 3
(e)
gold;
argyrol.
albumen; (c) cooked soap; (g) cooked starch; (h)

(b)
rubber;
(j)
11. Briefly explain
the mutual coagulation of colloidal
As 2S 3
and Fe(OH) 3
12.
Explain the coagulation of colloidal Fe(OH)., by 13. How may emulsions be stabilized?
NaOH.
DISPERSED SYSTEMS
371
14. Define or explain the terms (a) Brownian movement, (b) osmotic pressure, (c) hydrophobic colloid, (d) ultra miscroscope,
(e)
peptizer.
15. List
and illustrate five different types of dispersed systems. would the rate of diffusion of a hydrophobic colloid probably be affected by (a) temperature, (6) size of particles, (c)
16.
How
concentration of particles, (d) viscosity changes in the water produced by adding a neutral substance like glycerine. Explain each case very briefly.
17.
How
(b)
do you think the following

,
electrolytes
3?
would compare
(a)
in their effectiveness in coagulating
a negative sol of As2Sa,
NaCl,
CaCl 2
(c)
Na 2SO 4
(d)
AgNO
CHAPTER XX
SOLUBILITY
1.
The property
and important
of
in
it is
of solubility is one of the most interesting of physicochemical phenomena. Some phase
encountered frequently, not only in everyday life, but industry and scientific investigations. To remove from clothing a grease spot, a grass stain, or a smear made by sitting on a chocolate cream requires a different solvent in each case. Most chemical reactions occur in solution and appropriate solvents must be selected. Separations, both analytical and industrial, are effected chiefly by the aid of
differences in solubility. Molecular weights often cannot be determined by vapor density since the temperature necessary
for vaporization
may
be so high as to be inconvenient
01
cause decomposition;
we may then determine it in solution and must know, of course, how to choose an appropriate solvent. Again, materials for vessels should be made of sub-
stances as insoluble as possible in the liquids likely to be put therein. In order to understand such phenomena, it does not suffice to commit to memory a few simple rules, for the factors involved are numerous and often complicated,
be profitable, nevertheless, to consider some of the more important factors and to gain some notion oi the general methods of attacking these problems. 2, As a first step, we may recall the classification of molecuIt is likely to
lar types previously given (Chapter V, paragraph 13) intc nonpolar, polar, and ionic molecules. Each molecular type
crystallizes in a corresponding solid lattice, also set forth in an earlier chapter (Chapter V, paragraph 15). may recall
We
furthermore, the general nature of the process of solution for each of these lattice types (Chapter VIII, paragraph 2}
372
SOLUBILITY
373
and proceed now to a more detailed discussion of each. We shall find that not only is solubility determined by the type of molecule and intermolecular force, but also by its strength. By way of illustration of the variety possible when we are able to vary both the strength and the type of intermolecular
field,
we may
in
trated
Fig.
consider the system illus1, showing substances
sufficiently insoluble in each other to exist in distinct liquid layers. This is a truly stable system and does not depend for
Htpttftt
the existence of layers upon mere slowness of diffusion, but would be reformed even though the system were shaken.
Aniline
Molecules. 3. Nonpolar Molecules which are uncharged and nonpolar are

able to attract each other only because of disturbances produced by mutual interaction of their rapidly
trons.
Pcititioro-
ktfoicnt
moving elecThis disturbance has no exact
Phosphorus
counterpart in ordinary mechanical systems, but is remotely analogous to the interaction that would exist between
Mtreury
two vibrating tuning
forks.
The magni-
tude of the force between a pair of such molecules depends on the total number of electrons in the molecule and the looseness with which they are held; also
Fig.
1.
Seven stable
upon the closeness of approach possible before repulsion between them sets in. The force falls off approximately with the seventh power of the distance between the molecular centers, and therefore practically disappears when a pair of molecules are only two or three molecular diameters apart. When two molecules come sufficiently close to each other, "repulsion" sets in, with something like a tenth or twelfth power of the distance. Molecules are, of course, not absolutely rigid, hard spheres. Figure 2 illustrates how the attraction between a pair of molecules grows rapidly
liquid layers.
374
Ch.
XX
first as the distance between them diminishes and then turns very abruptly into repulsive force. A comparison of curves A and B shows how the substance represented by A may have a higher intermolecular attractive force at the same distance than the substance represented by curve jB;
at
nevertheless the force between the molecules for B may actually be greater at equilibrium than for A, on account of their closer approach to each other. It is not easy to
measure the force existing between single pairs of molecules, and it is actually more important, of course, to consider the total resultant forces existing
within a mass of liquid. This bears a relation, too complex to be explained here, to the
forces between pairs of molecules which shows that it is
possible to measure the total attractive energy existing within
a mass of liquid by the en-
gt
ergy of vaporization per cubic centimeter of liquid or the en-
ergy of vaporization per mole volume of the liquid at the temperdivided by the molal ature at which the vaporization takes place. Table 1 gives
values of the square root of this quantity, called "solubility parameters/' for a number of more or less familiar substances. few of them are substances which ordinarily exist as solids
which
at 25 C., and the values given are for the supercooled liquid, is unstable with respect to the solid at this temperature.
in order of increase in the values of their solubility parameters from the top to the bottom of the table.
The substances have been arranged
arrangement is that which have nearly identical solubility parameters are able to mix with each other with very little difference between the attractive forces of the like and the unlike
liquids
4.
The
significance of this order of
SOLUBILITY
773
given molecule, therefore, has about the same tendency to escape into the vapor phase from a solution as it would have from its own pure liquid hence the number of molecules in the vapor phase is proportional to the mole fraction of them in the liquid. This law, known as Raoult's Law, may be written
molecules.
;
p = p*x
where p equals the partial vapor pressure of the substance from the solution, p is its vapor pressure in the pure state and x is the mole fraction of that species in the solution. In cases where this law holds, it is possible to calculate solubility from the above equation, not only of vapors, but also for gases and solids. (Cf. Chap. IV, par. 14.) 5. The solubility of a gas is usually expressed in terms of the amount which dissolves when the gas is at 1 atmosphere
partial pressure over the solution. In such a case
p =
and
= l/p.
the pure gas over its boiling point of the
p is in this case the vapor pressure of own liquid and is higher the lower the
gas.
If the temperature in question lies above the critical pressure of the gas, of course p has no obvious physical fictitious value for it, however, can be derived meaning.
by extrapolating the vapor pressure above the critical temperature. For making such an extrapolation, a plot of
the logarithm of the vapor pressure of the gas against the reciprocal of the absolute temperature can be used; this gives a straight line from which the extrapolation can easily
some higher temperature. Table 1 contains, for the solubilities of three gases, hydrogen, nitrogen, illustration, and chlorine. Their boiling points increase in that order, and
be
to
made
the same order.
their solubilities, as will be seen from the table, increase in To put it in another way, chlorine is the gas
most easily condensed to a pure liquid and hydrogen is the one most difficult to condense. Correspondingly, chlorine is most readily condensed into a solution and hydrogen least
readily.
oo
CN 00 H
oo
I
IT)
IO \O
00 ro
(N 00 sq
q OO
10 ^H <N ' oq f-H <N Tf
00 <N
376
SOLUBILITY
6.
377
We
see
of hydrogen
eter.
from the values in the table for the solubilities and nitrogen, that these values decrease as we
go from liquids of lower to liquids of higher solubility param-
The explanation of this trend lies in the fact that the molecules of hydrogen and of nitrogen have very low fields of force, and hence they are able to penetrate most readily into liquids in which the forces of attraction between the
molecules are low.
As we descend the
table
to liquids of
higher solubility parameter, such as carbon clisulfide, it is difficult for hydrogen and nitrogen molecules to get in be-
tween the molecules of solvent, hence their solubility is low. Chlorine, on the other hand, although a gas at ordinary temperatures, has small molecules and we see from the value
of the energy of vaporization per cubic centimeters that the
attractive forces between chlorine molecules are rather high; consequently, this substance dissolves most readily in the
liquid nearest to
it
in the table,
and
its solubility falls off in
both directions.
7. Solids. Iodine, sulfur, and phosphorus have very high attractive fields; hence they mix most readily with liquids near them toward the bottom of the table, and their solubilities decrease as we ascend the table, the opposite order to that found for hydrogen and nitrogen. Accordingly, we could fill in missing values in this, or even in a more extended
with a considerable degree of confidence. For example, the solubility of sulfur in silicon tetrachloride should doubtteiblc,
less
be a
little
more than
0.3
phosphorus about 1 mole per cent.

8.
in silicon tetrachloride
mole per cent. The solubility of may be expected to be

in
The
solubility of
solid,
the absence of chemical

in a solvent
reactions, will
close to
normally be a
maximum
which
is
it in solubility parameter. This is true, for example, with sulfur and iodine, which do not react chemically. In such a case, the solubility in terms of mole fraction, x, can be calculated at a given absolute temperature, T, from the
heat of fusion per mole of the solid solute, AH, at
its
melting
378
Ch.
XX
point,
Tm
by the following equation

10g *
=
4.58
Tm T
'
The equation corresponds to the fact, which should be more or less obvious, that the higher the melting point of the substance and hence the harder it is to melt it to its own pure liquid, the harder it is, likewise, to get it to enter into
a liquid state in some other solvent; hence the solubility of a substance normally increases with temperature, and a substance with a lower melting point is more soluble. A large value for the heat of fusion of the solute likewise tends to diminish solubility. If we are considering a solvent anc/
a solute which have rather different solubility parameters, thei> the solubility will be normally less than that calculated by the above equation. This is illustrated by the decrease in
in the liquids higher
9.
the values for the solubility of iodine, sulfur, and phosphorus up in the table.
melting point on solubility is beautifully by the comparison, shown in Table 2, between phenanthrene and anthracene, two substances which have
effect of
The
illustrated
TABLE 2
Solubility
Molal
vol. cc.
Melt.
pt.
mole per cent at 25 C. in

benzene
Boil,
pt.
Phenanthrene
174
142
99.6
218.
18.6
340 342
000
Anthracene
0.63
the same composition, Ci 4 Hi but differ only in the arrangement of the carbon atoms as shown in the table. The hexagons of carbon atoms are in a straight line in the latter but not
,
The result is that the anthracene molecules much more closely in the solid crystal, as shown by pack the volume. They therefore attract each other more strongly,
in the former.
so that this substance both melts at a higher temperature
11
SOLUBILITY
in all solvents to
379
a far smaller extent. To appreciate this, you have only to recall how much better your trout fit your frying pan before they are cooked than they do later, when they curl up. It is interesting to note that
the two substances here considered, although they have very different melting points, have practically the same boiling point. This we may attribute to the fact that at high temperatures there
10.
is sufficient
and dissolves
thermal motion so that the liquid
in either case consists of molecules
jumbled up
in all positions.
two
interesting contrast in solubility is presented by forms of sulfur. The molecules of ordinary sulfur consist
An
of octagonal rings of atoms, represented in Fig. 3. These molecules retain their identity when dissolved. When these crystals are melted at 115 C., the
same octagonal molecules persist for a while. As the temperature is raised, however, the more violent agitation
gradually knocks the rings apart, with the formation of chains of varying lengths. These chains become entangled with each other, so that the liquid be-
comes very
viscous, quite contrary to the usual behavior of liquids on heat- &g- 3. Molecule of rhombic sulfur ing. If we heat the sulfur still further, it gradully becomes more fluid as the chains become shorter, but if suddenly cooled by pouring into water, the rings do not have time to reform and the chains are "frozen." The chains are zigzag and can be extended by pulling, and the mass
*
consequently behaves like rubber. The sulfur in this form is not soluble, since the chains are all tangled up like a mass of tangled string and small soluble units are not detachable. 11. Polar Molecules. Polar molecules cannot be expected to fit rigidly into the relation between solubility parameter and
in Table 1, and discussed in preceding In many cases, however, departures from the paragraphs. preceding regularities are absent or small. This is particularly the case for substances whose electric dipoles are fairly weli
solubility
shown
380
Ch.
XX
buried within the molecule, as is the case with ether and chloroform, which, despite their rather considerable dipole 18 moments, both 1.1 X 10" e.s.u., fit very well into the scheme
shown
10~~
18
,
fit at all well into that regular scheme. Dipole alone can therefore not be a safe guide to predict see in Table 3, first, that deviations from regular behavior.
Table does not

in
1.
However, acetone, with a moment of 2.85
moment
We
the solubility of propyl chloride in water at 20 is greater than that of propyl iodide, in accord with its larger dipole moment, provided that we apply them as pure liquids to the
water. However, that is not fair to propyl iodide, which has a much smaller vapor pressure, and if we remove the handicap
in the table,
by applying them both as vapors at the same pressure, 10 mm. we see that the iodide is more soluble.
Propyl chloride C 3 H 7 C1 Propyl iodide C 3 H 7 I Propyl alcohol C 3 H 7 OH
Nitrobenzene
Aniline
Phenol
C 6H 5NO2 C 6H 6NH 2 C 6H 6OH
Table 3 shows also that nitrobenzene and phenol, which must have nearly the same vapor pressures at 20 since their boiling points are not very different, are soluble in water to amounts quite out of relation to their dipole moments. The
explained in the following paragraph. dipoles present in water, the alcohols, ammonia, organic amines, and hydrogen fluoride are attracted to each other by exceptionally strong forces called "hydrogen bonds."
is
reason for this

12.
The
12
SOLUBILITY
381
This
is illustrated particularly in Fig. 4, where boiling points of certain series of compounds are plotted against molecular
weights. For most of the compounds shown, the boiling point increases with increasing molecular weight, but water, hydro-
gen
fluoride,
and ammonia have much higher
boiling points
400
r-
300
H,Te
200
100
23456
Period
Fig. 4.
Effect of hydrogen bonds
on
boiling point.
than would be expected on this basis. These liquids also freeze at abnormally high temperatures, forming solids having a peculiar type of structure. The structure of ice is indicated in Fig. 5. This is a comparatively open structure, with a density less than that of water. Each atom of oxygen is surrounded by four others, and atoms of hydrogen are on a line between the atoms of oxygen, although nearer one atom of oxygen than the other.
382
Ch.
XX
a substance, in order to be soluble in water, of tearing apart the hydrogen bonds and the substances here under discussion all readily mix with each other. Nonpolar molecules, however, or even those conIt follows that
must be capable
Structure of ice. The light spheres represent oxygen atoms, the dark Fig. 5. ones hydrogen. It is evident that melting, which partly breaks up this structure, permits a closer packing and therefore higher density.
taining ordinary dipoles, often fail to penetrate the structure of water. Referring again to Table 3, we see that propyl alcohol
has nearly the same dipole moment as propyl iodide, but that whereas the latter has very limited solubility in water, the former is completely miscible with water, due to the fact that
its
hydroxyl groups are able to take part in the structures
13
SOLUBILITY
383
appropriate to water. Again, in Table 3 we see the dipole moment and solubility in water of the three substituted
benzenes, nitrobenzene, aniline, and phenol. Their relative solubilities in water evidently have no relation to the dipole
moment, but they do accord well with their ability to form OH of phenol entering hydrogen bonds with water, the most readily into the structure and the NH2 of aniline less
readily.
The
most polar of
nitro group of nitrobenzene, although it is the all, does not help a great deal in bringing nitro-
benzene into solution in water. 13. Electrolytes. The nature of the process of solution of a salt was illustrated in Chapter VIII, Fig. 1. It is evident from this that the solubility of a salt is favored by high dielectric constant on the part of the solvent, and therefore water and ammonia are particularly effective. In order to compare the solubilities of different salts, let us break up the process of the solution of the solid in water into two
steps: first, the separation of the ions of the solid crystal into gaseous ions, and then the hydration of these ions by
bringing
them separately
(s)
into water.
MX
but
it
->
M+
is,
(g)
+ X- (g)
->
M+
(aq.)
+ X- (aq.).
Such a process
is
of course, not easy to realize practically,
quite legitimate to consider it theoretically. The energy required for the first part of this process, that is, the separation of the solid ions into gaseous ions, is called the
energy of the substance. This process was one of the considered in Chapter V, Table 7 and Fig. 8. The amount steps of energy that must be put in for this step in the process evidently depends, first, upon how close the solid ions are
lattice
lattice; second, upon their charge; third, upon the nature of the ions themselves for example, whether their kernels have 8 or some other number of outer electrons. Kernels with 18 electrons are, as it were, softer, more deformable, and can get closer to ions of the opposite charge than kernels containing fewer electrons. The energy recovered in
in the
the second stage of the process, the hydration of the gaseous
384
ions,
depends on the
size
Ch.
XX
of
the electron kernel.
and charge of the ions and the nature The same factors, therefore, tend
assist the solubility insofar as the second step in the process is concerned, and to oppose it in the first. However, the different steps do not operate in quite the same way in the two cases, and the net result differs for different
both to
substances. It
is
obvious here, as in so
many
other cases of
physicochemical phenomena, that no extremely simple rules can be formulated. A few illustrations will show, however,
the usefulness of the above scheme of analysis.
TABLE 4
Hydration, Solubility, and Ionic Size
for Sulfates of the
Type,
MSO
g.
lon
Radius
H O in
2
Solubility
g.
10* cm.
solid
per 100
HO
2
SO4
Ba++ Pb++
Sr++
3.0
1.4
1.3
0.0002 0.004
0.01
1.15
1.0
Ca++ Fe++
2
7
7.
0.2
21.
27.
0.8
Mg+ +
14.
0.75
sulfates of
In Table 4 are given the solubilities of a series of doubly charged positive ions, together with the
solid crystal
water of hydration of the

ions.
and the
radii of the
The
sulfate ion
it
,
is is
ions with which
of course larger than any of the positive combined. The smallest positive ion
of the series,
does not by itself fill up very well the between the sulfate ions, and there is room for 7 molespace cules of water around each magnesium ion. Even in the
solid state, the
Mg+ +
magnesium sulfate is already largely hydrated and it is an easy process for the ions to be further separated on going into solution; that is, the substance is very soluble
the size of the positive ion increases, however, in ++ we arrive at a substance going finally to barium ion, Ba
in water.
,
As
whose two ions have more nearly equal size and which can pack firmly into a solid crystal, with no need for water to fill it out. The result is an extremely insoluble substance.
15
SOLUBILITY
TABLE
5
385
Substance
Ions
Radii
X IP cm.
24
0.00003
NaCl
Na+,
Gh
CuS
15.
Cu++
S~
effect
1.0, 1.8
1.0, 1.8
The combined
is
of
in
ionic
charge and a many5,
electron kernel
comparing NaCl and CuS, both of which have the same crystal structure and
illustrated
Table
practically the same ionic radii. The greater attraction of the ions of CuS for each other is attributable, first, to their
double charge, which, according to Coulomb's Law, means 4 times the interionic attraction at equal distances; second,
to the greater interaction of the larger
number
of electrons.
The
evidently
greater strength of hydration, due to these same causes, is not sufficient to offset the large lattice energy.
CHAPTER XXI
CARBONIC ACID AND

1.
ITS
IONS
in this
ion,
bi-
book to carbon
Frequent reference has been made elsewhere dioxide, carbonic acid, carbonate
carbonate ion, and insoluble carbonates. The purpose of this chapter is to amplify this material into a coordinated whole; first, because it can afford excellent practice in applying the principles of chemical equilibrium; second, because these substances are involved in an extraordinary number
of interesting industrial, geological, and biological processes. These include industrial preparation of sodium carbonate and bicarbonate in huge tonnages, the solution of limestone rock by ground water, forming limestone caves, and the
redeposition of crystalline calcium carbonate as stalagmites; the formation of marine shells, pearls, and coral rock from sea water by marine organisms; the formation of egg-shells;
the "softening" of "hard water" for industrial or laundry use; and the buffer mechanism which maintains the blood at constant alkalinity. 2. Carbon dioxide molecules have a linear structure, OCO.
The most probable electron structure is indicated by the O that is, the carbon and oxygen are C formula O double bonds (cf. Chapter XVIII). If the bonds joined by
: :
consisted of ordinary electron pairs, the tetrahedral bond angles characteristic of carbon would be found and the
molecule would be unsymmetrical and show a dipole moment (cf. Chapter V, paragraph 14; Chapter XXIII, paragraphs
12, 13).
3. Physical Characteristics. Liquid CO 2 is available commercially in steel cylinders. It has a vapor, pressure of 59 atmospheres at 20 C. If the cylinder is tilted so that liquid
386
CARBONIC ACID AND
ITS
IONS
387
instead of gas escapes through the valve, part of this liquid vaporizes, cooling the rest sufficiently to form solid, which can be caught in a cloth bag. This solid has a vapor pressure
of
1
atmosphere at
78.5
C., therefore it
sublimes without
2 is known as "dry ice," and is much used melting. Solid for refrigeration. It melts at 56 C. under a pressure of 5.3 atmospheres. When liquid and gas sealed in a stout glass tube are heated, the liquid phase expands and the
CO
gas phase becomes more concentrated till finally their densities are identical and the meniscus of separation disappears at 31.35 C., the critical temperature. The pressure at this
is 73 atmospheres. Carbonic Acid. The solubility of CO2 in water at a C. partial pressure of one atmosphere at temperatures of to 30 C. is shown in Table 1.
point
4.
TABLE
Solubility of
CO
at 1
Atmosphere
15
in
Water
25
1.49
tC.
g.
10
liter liter
20
1.72
30
1.31
per
3.32
2.35
2.00
moles per
0.076
0.053
0.045
0.039
0.034
0.030
the solubility at other pressures can be calculated approxi-
mately by Henry's Law (cf. Chapter III, paragraph 19). It is convenient to remember that about 1 liter of CO2 dissolves in 1 liter of water at 20 C., regardless of the pressure, since the volume of gas and the weight of it which dissolve in 1 liter are both proportional to the pressure.
Equilibrium
is
attained rather slowly, since part of the

1
CO2
reacts
somewhat slowly with water to form about
per cent of
H 2 CO3 as follows: C02 + H 2 = H 2 C03 = H+ + HC03~
water has only a very mild acid evidence that the above ions are formed only in very low concentration. The concentration of H+ can be determined, among other ways, by the aid of indicators sensitive within the proper range. Methyl orange, for example, shows an
fact that plain soda
The
taste
is
388
Ch.
XXI
orange color in solutions of CO2 at 1 atmosphere pressure 10~ 4 To perform an accurate experiment, indicating (H+) one should make up a series of buffer solutions (cf Chapter XIII, paragraph 51) in steps covering the desired range, add uniform amounts of indicator to the buffer solutions and to the carbonic acid solution, and determine the best color match under conditions of equal solution depth and
.
.
illumination.
Another method
is
to measure the e.m.f. of
a hydrogen electrode in a solution of
CO2
(cf.
Chapter XV,
paragraph 22).
Now the
the second
always ionizes much less easily than the first. We may connect this with the This much greater attraction of the doubly charged CO3 is easily confirmed by experiment. The solubility conclusion
.
other ion must be mainly + of a weak dibasic acid
HCO
3 ~",
not
CO
for
of
product is (Ca++ ) (CO 3 ) = therefore 0.1 M-Ca++ can detect CO 3 in any 4.8 X 10~ 8 concentration greater than 4.8 X 10~ The fact that CaCl 2
CaCO3
is
,
very small, and
its
"
(aq.)
forms no precipitate when added to 0.034
M-CQ2
indicates that the concentration of

is
CO3
in this solution
than the concentration of the H+, which is ap4 4 proximately 10" at 25 C., more precisely, 1.2 X 10" The state of affairs in the solution can therefore be sumfar less
.
marized as follows:
CO2 (latm.)
+H O 0.034 M
2
)
= H 2 CO 3 =
H+
1.2
+
1.2
lO^JIf
less
The (CO3
the (OH")
5.
in this solution is
is,
of course,
much 4 lO^/lO" or
than 10~4
M and
lO'
10
M.
is
The
first ionization
constant of carbonic acid
(H+)(HC0 3~)
(H 2 C0 8 )
x
where we understand that (H 2 CO 3 ) represents both the
H CO
2
CARBONIC ACID AND

dissolved
ITS
IONS
1.2
389
and the
1.2
CO
4.3
2.
10-V0.034
The above
10~7
.
figures yield
10" 4
6.
Sodium Carbonate
Solutions.
till
Let us consider next
solutions of
Na 2 CO 3
leaving
later the
.
more complicated
NaHCO3 Since there is not CO2 to precipitate Ca++, the ~ second ionization of carbonic acid, HCO3 = H+ + CO3 must be extremely weak. Solutions of CO3 must, therefore,
intermediate case of solutions of
enough
CO3
in solutions of
be strongly hydrolyzed (cf. Chapter XIII, paragraph 25) and this is indeed the case, the reaction being
CO3
If
1
~+HO
2
, ,
HCCV +
OH"*.
salt,
we
use 0.5 Af-Na2 CO3
which, as a strong
contains
we find, on careful investigation Af-Na+ and 0.5 M-CO3 with a suitable indicator, such as alizarin yellow R, that
(OH")
0.01
M. This
alkaline reaction
is
responsible for
many
7.
important uses of
Na2 CO 3
calculated
The second by the

and
~ thus liberated, one molecule of HCO 3 was formed, hence (HCOs") = 0.01 M. This leaves (CO 3 ) = 0,49. Now
Na 2CO 5
ionization constant of carbonic acid can be aid of the above figures. took 0.5 mole of found 0.01 mole of OH"". For every molecule of OH~
We
(H+XCO, A2 _
and (H+)
(HCOO
,
10- 14 /(OH-)
10~ 12 hence,
10~ 12
X *
0.49
4.9
10-"
This agrees closely with the accepted value, 4.7 X 10~ u In reality, small differences in temperature cause greater variations than this.
.
we have
Solutions. If we use 1 Af-NaHCO3 , in solution primarily 1 M-Na+ and 1 Af-HCOs", but the latter can undergo two further reactions. It is a weak acid, therefore it can ionize according to reaction (a) below.
8.
Sodium Bicarbonate
But
it is
also the ion of a
weak
acid,
and can therefore hydro-
390
shown
(a)
(6)
Ch.
XXI
lyze as
in (&).
= H+ + CO3~ HCO3HCCV + H 2O = OH- + H 2 CO3
If
(a)
alone occurred the solution would be weakly acid
(^K^) and if (6) alone occurred the solution would be considerably more alkaline than a solution of sodium acetate, because H 2 CO3 is a much weaker acid than acetic acid, as _ anyone can see by comparing the tastes of soda ~~ HCO " water an d vinegar; just how much, an underHCO 3~ standing student would see7 from their ionizaHCO 3 ti n constants, 4.3 X 10~ for H 2 C03 and 5 CO 3 1.8 X 10~ for acetic acid. But since reaction H+ < HCOs~~ (a) liberates H+ and reaction (b) liberates OH", HCO 3 these neutralize each other, causing both more HCOa" CO 3 and more H 2 CO 3 to be formed than be formed by either reaction alone, while HCOa^ would
~"
+ or OH~ from increasing preventing either very much. Indicator tests on a solution of ~ 6 therefore reaction 1 Af-HCO 3 show that (OH") = 2 X 1CT a little over (a). The net result of both (b) evidently gains
3
(a)
and
(6) is
mainly
2
HCOjf = CO3
0.98
~ + H CO
2
Equilibrium
cones.
.01
.01
There
is
a somewhat different
way
of understanding this
result without invoking the role of water. In a solution con~~ 3 ions, an occasional H+ splitting off taining many
HCO
HCO3~~, there are so many more HCO3 ions that the a good chance of uniting for a while with one of them, 1. forming H 2 CO3 as illustrated by Fig."~ It is obvious that, left behind, except is formed for every CO 3 one H 2CO 3 as altered by the watery which is very little.
that of
partner, but almight find its way back later to its CO3 for H+ is much stronger than though the attraction of CO 3 ~
H+ has
11
9.
CARBONIC ACID AND

The
ITS
IONS
391
equilibrium constant of the bicarbonate equilibrium
by eliminating (H+), which gives
(HtCOa)(CO~)
K*
Xi
1,
4.7
""
(HCO
If
3 -)
4.3
(HCO 3")
10.
is
chosen as
then (H 2
X X 10~ CO ) = (CO
7 3
10" 2
as
given above.
Displacing the Bicarbonate Equilibrium. Removal of CO3", as by adding Ca++, of course increases (H2 C03 ) till it becomes sufficiently large to stop the reaction at a new
set of equilibrium concentrations. 2
HCOjf
Ca++
Ca++
This
is
" + CO " + 2 HCO

3
3
= CO 3 ~ + H 2 CO 3 = CaCO3 = CaC03 + H 2 CO3
Adding the reactions gives
_
2X
10*.
of limestone
right to
the important equilibrium involved in the solution by natural water, the equation as read from
left,
reprecipitation by loss of CO2 such as occurs in the formation of stalagmites in limestone caves, or on boiling this variety of "hard water," forming scale in steam boilers and kitchen kettles.
and
its
equilibrium constant for this reaction can be obtained by combining the constant for the pure bicarbonate equilibrium with the solubility product of CaCO 8 We write
11.
.
The
(H,CO,)(CO,
-
=
4.8
(HC0 8~)
and
(Ca++)(CO~) =
(H 2 CO 3 )
10-.
Dividing the former by the latter gives

2
(Ca++)(HCO 3~)
As an example
in
X 104.8 X 10-*
10
6
of the use of this constant,
we may calculate
a solution of limestone in water charged with carbonic acid from 4 pure air, in which the partial pressure of CC>2 is 3 X 10"" atm.
392
a. XXI
Taking the concentration of H 2 CO 3 when the pressure of COf ia 1 atm. as roughly 0.04 (cf. Table 1) then, when the partial pressure
of
to 0.04
10~ 4 atm., the value of (H 2 CO 3 ) is reduced reduced to 3 3 X 10-4 = 1.2 X 10~ 6 which we may introduce into the above equilibrium constant. We see from the equation that ~ 2 HCO 3 are formed along with each Ca++, therefore (HCOO = 2 (Ca++). Substituting these values in the above equation gives
2
CO
is
X
which yields (Ca ++ )
1000
liters,
,
_ ~
10~ 4
.
X x
10 4
'
A cubic meter of surface water, over limestone, could dissolve 0.53 mole or flowing 5.3 g. of CaCO 3 and this amount of hard water, evaporated in a steam boiler, would deposit 53 g. of boiler scale. If used in a
5.3
laundry,
it would destroy the equivalent weight of soap. If the soap were pure sodium oleate, Ci8H 33O 2 Na, this would weigh 322 g. It is evidently important to "soften" hard water by removing this Ca++.
12.
of
Water Softening. Hard water formed by the solution limestone as above can be softened by (1) boiling, a pro(2)
hibitively expensive method,
neutralizing the
H 2 CC>3,
by hydrolysis, inmonosodium phosphate, sodium cluding ammonia, borax,

using any
alkali or salt reacting alkaline
Ca(OH) 2 can be used under analytical control so as to get the exactly equivalent amount. Hardness due tc
silicate.
dissolving CaSO 4 such as Na2CO 3
must be removed by adding a
precipitant^
An
artificial
or natural zeolite, which is
insoluble in water, can exchange its reaction:
Na+
for
Ca++ by the
Ca++
+ 2 NaH 6 AlSi0 =
7
Na+
it
Ca(H 6 AlSiO7 ) 2
When
the material
ion
is
exhausted,
can be regenerated by
washing with concentrated brine.
Magnesium
water and
13.
its
may
also contribute to the hardness of

is
similar to that of calcium ion. chemistry principal equilibrium in a solution of NaHCO 3 , ~ ~~ H 2 CO3 is shifted by boiling or even. 2 HCO3 = CO 3 on standing exposed to the air, since the equilibrium con-
The
15
CARBONIC ACID AND
ITS
IONS
393
centration of 2 CO3 in pure 1 M-NaHCO 3 is 0.01, while the CO2 in pure air can maintain only (H 2 CO3 ) = 1.2 X
Consequently, although the (OH~~) in a pure solution 6 10~~" (cf. paragraph 8) it rises on standing exposed to air, or rapidly on boiling the solution, increasing the
is
5 10"" .
(CO3
which, as
we have seen (paragraph

If solid
alkaline reaction.
NaHCO 3
are evolved, and Na2 CO 3 is left by above: 2 NaHCO3 = Na2 CO3 2O
6) gives a strongly heated, 2 O and CO2 a reaction similar to the

is
+H
+ CO
Summary. Let us now collect, in Table 2, the knowledge we have gained concerning the concentrations of the various substances present in solutions of CO 2 NaHCO 3 and Na 2 CO 3
14.
, ,
TABLE 2
Solution
1
Principal
substances present
Present in smaller concentrations
atm.
.03 Jl/-H 2
CO 3 + CO2
1(T 4
M H+
Af-NaHCO3
^
1
M-Na+ 1 M-HCOs" (0.98 M)

Jlf-Na+
0.5
0.01
.01
(OH~) =
.01 .01
0.5
Af-Na2 CO,
M-CO~
M-OH"
(0.49
M)
The numerical values in this table are worth remembering. This is made easier by the fact that .01 occurs in several
places. IS. Plot of
pH. Fig. 1 gives a further graphical insight into the nature of these solutions. It represents the values of log (H+) or pH for solutions made by starting with 1 liter of 1 Jlf-NaHCOa and adding, on the one hand, fractions
of a liter of 1 If-NaOH, giving eventually 0.5 lf-C03 and, on the other hand, fractions of a liter of 1 If-HCl, to give 2 CO3 and then an excess of H+. This plot reveals in graphic form a number of the points brought out in previous dis,
The points of inflection represent the values of for pure 2 3 3 3~, and respectively, although in the case of the last we have assumed that the COa formed
cussion.
CO
HCO
H CO
pH
394
is
Ch.
XXI
kept in the solution under pressure, giving (H 2 CO3 ) = 0.5 M, not 0.04 M, as when the CO 2 is at 1 atmosphere. We see, also, that the curve is very flat in the intermediate
ranges so that these solutions could serve as buffers Chapter XIII, paragraph 51). The buffer containing
HCO3~
(cf.
and
H C03
2
is
responsible for keeping the

14
12
extremely important to man for it is partly pH of the blood at its normal
10
6
4
0.5
0.5
Moles
OH"
Moles H"
on adding to 1 liter of 1 If-NaHCOj, fractions of a liter Change in Fig. 1. of (a) 1 If-NaOH (to the left of 0), and (b) 1 M-HCl (to the right).
pH
value of about
This buffer action is so reliable as to the anxiety of many people over "acidosis" make unnecessary and the "acid ash" of foods, stimulated by skillful commercial
7.4.
advertising designed to sell at a high price sodium bicarbonate disguised under various brand names.
could be determined The curve shows, also, that CO3 with acid using an indicator changing at between by titration pH 8 and 9, indicating one equivalent of acid, or by one changing at about pH = 3, for two equivalents of acid. The curve is much steeper for the latter change, so that the end
point would be sharper. Combinations of NaOH and Na2 CO3 or of Na2 CO3 and NaHCO3 can be analyzed by getting
both end points.

16. Disposition of
CaCO by Marine
3
2 (Ca++) in sea water -is given as 10"
M.
Organisms. The value of Since (Ca++) (CO 3""~)

,
round off to 5 X 10~ 9 it is necessary, in order to precipitate CaCOt from sea water, to have (CO"""")
4.8
10~ 9 which
,
we
will
17
7
CARBONIC ACID AND

, ,
ITS
IONS
395
If this must be obtained from the dissolved be necessary for (H + ) to be less than a certain 2 value. Let us calculate this value. The (H 2 CO 3 ) in sea water we can calculate from the partial pressure of CO 2 in pure air, 3 X 10~ 4 atmosphere, and its solubility in water at 1 atmosphere and 25 C., which is 3.4 X 10~ 2 M, according to Table 1. We will assume tropic
= S X 10~ at least. CO it will, of course,
7 necessary to give (CO 3 ) = 5 X 10~ in the presence of (H 2 CO 3 ) 6 = 10~ we may substitute these values in the expressions for KI
,
water. In sea water, accordingly, we should find that (H 2 CO 3 ) = 10~6 approximately. In order to calculate what value of (H+) is
and #2, paragraphs 5 and 7, getting (H+) (HCO 3~) = 4.3 X 10~ 12 and (H+) = 10~4 (HCO3~). Eliminating (HC03 ~) gives (H+) 2 = 4 X 10~ 16 and (H+) = 2 X 10-. Evidently the organism must be
able to establish a slight alkalinity in order to deposit CaCO3 if it has to depend solely upon the dissolved CO 2 Since, however, it produces CC>2 by its own metabolism, the (H+) may be somewhat
.
higher and
still give a sufficient (CO 3~~~). Conversely, it follows that coral rock should dissolve in sea 8 water, in which (H+) > 2 X 10~ be recognized, of course, that such a calculation as the It should
.
above
should
is
all
only approximate and exploratory. The equilibria involved be affected not only by temperature, but also by the
other constituents present in sea water and by the biochemical composition of the secreting organs of the animal. Nevertheless, no one could properly investigate the physiologic process who does not understand the basic inorganic chemistry involved.
17. The Solvay Process for the manufacture of sodium carbonate and bicarbonate is an interesting example of one which is successful by reason of using cheap raw materials,
low energy
reaction
is
costs, and little waste by-product. The central the precipitation of solid NaHC03 from its ions at C. The at low temperature. Its solubility is 0.82 ~ from the reaction: Na+ comes from NaCl and the 3 + CO2 = 2O 4 3 ~. The CO2 comes from 3
NH + H
NH
HCO + HCO
"burning"
CaC03
and the
by demand
the action of
for
Ca(OH) 2
3 is recovered from the obtained from the limestone.
NH
NH 4+
The
Na2 CO3
is satisfied
ing the liberated
CO2
returnby heating to the process. The only waste product

,
NaHCO3
396
is
,
Ch.
XXI
CaCl 2
for
which there
is
process and the coordination between in a flow diagram, Fig. 2.
some market. The steps in the them are represented
NaHCO,
CaCl z
Products Fig. 2.
of
Diagram
Solvay Process.
Exercises
See Appendix
1.
II for
answers
solutions ; (c) 0.5
of (a) 0.034 Jlf-Na 2 3
Write equations Jf-H 2 CO 3
for the principal equilibrium in

(or
CO
aq.);
(ft)
^-NaHCO 3
CO
2.
Give
the
present in the
approximate concentration of each substance above solutions.
3. Can the following substances be present at moderate concentrations, say 0.1 molal, in the same solution? If not, what is
formed?
H CO and H+, H CO and Ca++, (c) H CO and HCOr, " HCO and H + (e) HAc and CO (/) Ca++ and NO S", (g) (d) ++ and SO OH" and HAc, (h) H CO and COs () Ca (j)
(a)
2
3
(ft)
2,
NH
4.
5.
and OH"". Give equations
for all pairs in question 3
How
will the concentrations of

3
tion of
(c)
NaHCO
be altered by
(a)
adding CO2, (d) adding more NaHCO 3 (e) boiling? 6. Write equations showing what happens in each of the follow,
which react. and CO 3 in a solu2 3 CaCl 2 (ft) adding NaOH, adding
H CO
ing cases: (a) Solid
NaHCO
NaOH,
is
with one of Na 2 CO3, (d)
(c)
is
CO
gas
solution of 8 is mixed heated, (ft) Solid CaSO4 is treated with a solution of passed into a suspension of CaCOi.
NaHCO
CARBONIC ACID AND

7.
ITS
IONS
397
Certain of the following pairs react to a considerable extent in 0.1 molal solutions; write the formulas of the substances formed in such cases.
when mixed
(a)
(d)
(g)
H+ and H 2 CO 3 (6) HCOr and CO. (c) Ca++ and H 2 CO 8 Ca++ and C 2 O 4~, (e) OH~ and CO 8 (/) H+ and CO,, Ca++ and Cl~, (h) HAc and HCO 3-, (i) Ba++ and NH 4OH.
,
~
,
8. How can you prove that the main reaction ~ water produces HCO 3 rather than CO 3 ?
of
CO
with
9. What volume of CO 2 gas, measured at standard conditions, would be produced by heating 21.0 grams of NaHCO 3 ? 10. One mole of CO 2 gas is passed into 1 liter of each of the
following: (a) water, (6) 0.01 Jlf-HCl,
M-NaHCO
extent
2 2
3,
(e)
0.1
M-KC1. Arrange
2
(c) 0.001 (d) 0.1 in order of the increasing
M-KOH,
is to which CO CO + H O = H+ + HCO
used
3-.
up according to the reaction:
11. The concentration of OH~ in 1 M-NaHCO 3 is less than M-NaAc. Does this agree with the relative strengths of the acids H 2 CO 3 and HAc? Explain.
1
12.
Why
What
is
NaHCO
"baking soda" and
Na 2 C0 3
"washing
soda"?
the relation between the equilibrium constant, K, ~ = CO 3 and the two ioniza2 CO 3 3 tion constants, K\ and Kt for carbonic acid?
*13.
is
for the reaction, 2
HCO
3
*14. If
will
M-NaHCO
)
is
shaken with
CO
at
atmosphere, what
(CO 3
become?
3 8 Using the values Ki = 7.5 X 10- and K 2 = 6.2 X lO" and second dissociation constants of H 3 PO4, calculate ~~ = H 3 PO 4 (a) the equilibrium constant for the reaction 2 H 2 PO 4 in 0.3 M-NaH 2 PO 4 + HPO 4 and (b) the concentration of HPO 4 *16. What will (H + ) be in soda water charged with CO 2 at 4.0 atm. at 25 C.?
*15.
for the first
*17. *18.
be in a solution made by passing CO at (H M-NaHCO ? *19. If the pH of blood is 7.4, i.e., log (H+) = - 7.4 = 0.6 - 8 and (H+) = 4 X lO"8 what is the ratio, (H CO )/(HCO -)? *20. What is the effect on the pH of blood of forced, rapid breathwill
What What
will
(OH-) be when (CO,~ )/(HCO,)+

)
3
0.4?
2
atm. into
0.1
ing?
*
difficulty.
398
and
in
Ch.
XXI
*21. Calculate
of Ki, -K 2
note
that
see
(OH~) in 1 Af-NaHCO 8 at 25 C. from the values KW1 and instead of setting (H 2 CO 3) = (CO 3 ) = (OH") - (H+). Do reality (H 2 CO 3 )
,
(CO)
you
why?
CHAPTER
XXIt
ACID-BASE SYSTEMS
1.
Resume
of the
Water System
of Acids
and Bases. Acids
and bases have
recent years usually been defined as explained in Chapter V, by their properties in aqueous solutions. In general, acids taste sour, they react with base metals
till
to liberate
and with carbonates to

'
liberate
CO2
and they
give characteristic colors to a class of highly colored organic substances called 'indicators," and they neutralize bases,
their "opposite numbers." They are compounds of hydrogen which ionize in water to give hydrogen ion, usually written called H+, or, more explicitly, H+(aq.), but also 3 0+,
"hydronium ion," with its assumed single molecule of water + ammonium ion. of hydration, in analogy with 4 2. Most bases are rather insoluble in water, so that they
NH
are experimentally
ize acids, as
marked chiefly by their ability to neutralshown by the disappearance of the sour taste, the
few soluble characteristically acid colors of indicators, etc. bases exist, including the hydroxides of the "alkali" elements
of group
1,
the "alkaline earth" elements of group

(cf.
2,
ammo-
nium hydroxide and organic amines

concentrations, give their
Chapter XVIII,
paragraph 20). These not only destroy acids but, in higher
own
characteristic colors to ap-
propriate indicators, and they precipitate the insoluble bases. They are hydroxides, and insofar as they go into solution
and the OH"" of bases neutralize each other instantaneously when mixed to form water, the solvent used in excess of all others, the historical system of acids, bases, and neutralization is this "water system."
Degrees of acidity and alkalinity of solutions are expressed
399
yield hydroxide ion, OH". 3. Since the H+ of acids
400
in
by the
1.0
Ch. XXII
terms of the concentrations of
course,
Kw
have seen, further, how certain substances, although containing no ionizable hydrogen or hydroxyl, can produce acid or alkaline reactions by hydrolysis, uniting with one of the ions of water and liberating the other (cf.
11-13).
X We
H+ and OH~, related, of dissociation constant of water, (H+) (OH") = 1(T 14 at 25 C. (cf. Chapter XIII, paragraphs
Chapter XIII, paragraphs 23 ff). All of this is adequate for the treatment of aqueous solutions both qualitatively and
quantitatively, and, in the opinion of many teachers, provides the most satisfactory approach to the subject for elementary
students of chemistry.
It
is
desirable,
somewhat later stage, although more or less
to
become
nevertheless, at a familiar with several other
related systems, each of
which
offers
certain advantages in dealing with certain types of acidic and basic substances or with reactions in certain solvents.
The remainder of this chapter was written for that purpose. 4. The Ammonia System. Liquid ammonia is one of the
best electrolytic solvents after water
(cf.
Chapter VIII,
it
paragraph
17).
Many
salts dissolve in it to give electrically
conducting, ionized solutions. Acids react with
to give
NH
more strongly than they do to 4 +, give OH3+, "hydronium ion," in water as a solvent. Moreover, we can have far more confidence in the correctness of
ion, far
ammonium
the formula
we can in the formula 3 +. The molecules in both liquid ammonia and water are connected to each other through hydrogen bonds or bridges (cf. Chapter XX, paragraph 12) but the bonds are much stronger in the
4
NH
+ than
OH
case of water.
The approximately right-angled molecules of water tend to unite with each other indefinitely to form the ice structure, except as interfered with by thermal agitation, which may be indicated in two dimensions as follows:
H 6 H O H H
:
H
:
H
:
H 6
:
etc.
ACID-BASE SYSTEMS
401
An extra hydrogen ion can add onto a pair of unoccupied electrons of a water molecule, but unless that molecule were thereby detached from the neighbors to which it is already
in writing forces, we would hardly be justified + while 3 excluding O 2 5 +, etc. In the case of 3 to ammonia, however, the bonds uniting 3 are so much weaker, and the bond between 3 and H+ so much + is 4 fully justified. stronger that 5. Pure liquid ammonia is a definite, if feeble, conductor, about 0. 1 as good as water, but its ions, for the reasons given
bound by strong dipole
OH
NH NH
NH
NH
2 ~, by analogy above, cannot be considered as H+ and + and with water, but rather 2 ~~. In this solvent, 4 4 NO 3 is an acid and therefore, a salt such as 2 is a base. These and analogous compounds potassium amide, can be titrated against each other with phenolphthalein, can be titrated in aqueous solution 3 and just as with the same indicator. The neutralization equation can be written ~ + = 2 4 2 3
NH
NH NH
NH
KNH
HNO
:
KOH
NH + NH
NH
6.
Amides can be changed to imides and
nitrides
by
losing
ammonia
more
just as hydroxides can be dehydrated in one or steps to form oxides:
KNH 3 KNH
2
2 2
= =
K NH + NH K N + 2 NH
2
3.
3.
By pursuing the analogy between the ammonia system and the water system, an extensive chemistry of reactions in liquid ammonia has been developed and systematized. These studies have yielded occasional by-products of significance " for ^quo-chemistry. One of the most interesting is an explanation of compounds such as HgNH 2 Cl, whose nature was formerly very puzzling. It is now regarded as "ammono'
basic mercuric chloride/' the

in
NH
being analogous to
OH
MgOHCl.
7.
Other systems based on the ions of the solvent,

the water and
systems,, suggest themselves having a sufficiently high dielectric constant to
like
ammonia
for solvents
402
Ch. XXII
give ionized solutions but which are themselves so weakly ionized as to be formed by "neutralization" reactions. An
acid would be defined as a substance giving the positive ion of the solvent, a base, one giving the negative ion. This has never proven to be a useful point of view, however, largely because it is too restricted, and overemphasizes the role of the solvent.
8. The Proton-Donor-Acceptor System. The majority of substances deserving to be called acids contain ionizable hydrogen. There are, consequently, a great many molecular species in addition to OH" which can unite with and therefore more or less neutralize H+. This has encouraged the development of a system in which OH" loses its special role as a
TABLE
Relative Strength of Inorganic Acids
and Bases
base and H 2 O its unique significance as a solvent and in which the sole criterion of acid and basic character is con+. sidered to be the gain or loss of a proton, unsolvated According to this point of view, an acid is a substance having + to another the chemical property of losing a proton,
substance, and a base is a substance, conversely, which is capable of adding a proton. These definitions hold regardless of whether the particular molecular species in question is
an ion or a neutral molecule. The examples in Table 1 should make these terms clear. 9. Since unsolvated protons do not exist in water and most other solvents, most actual acid-base reactions consist
11
ACID-BASE SYSTEMS
403
in a transfer of the proton from the stronger acid to the conjugate base of the weaker acid, illustrated by the ex-
amples in Table
2.
TABLE 2
Acid-Base Exchange Reactions
Acid
A Hcio4
NH +
4
H O+ Hsor
3
+ Base B + Ho + OH' + CHsCOCT + Hcor

2
= = = = =
Base
cior
NH
2
+ Acid B + H o+
3
so 4
HO ~
H + CH COOH + H 2 co
2
3
The
greater the disparity in strengths the larger the equilibrium concentrations of the species on the right. 10. This method of regarding acidic and basic properties
does not require the concept of hydrolysis to explain either + or the basic character of CO the acidic character of 4 3
NH
emphasizes the basic character of 3 in = its own right as due to the reaction, H+ 3 4 +. does not limit that character to its aqueous solution as It
Furthermore,
it
+ NH
2
NH NH
4
due
liberating
NH + OH". At the equation, NH + + H O

=
+ 4
4
2
OH" by
the reaction, the same time,
NH + H O
3
NH OH
it
3
NH +
permits us to write H 3 O+, practically
identical with the hydrolysis equation as ordinarily written,
understood to be H+(aq.), equivalent to H 3 O+. The fact that only in a very little 4 3 is formed, in the one case, or the other, is explained by saying with respect to the former, either that 4 +, or, 3 O+ is a much stronger acid than is a much stronger what amounts to the same thing, 3
2
NH 4+ + H O = NH OH +
4
H+,
where the
H+
is
NH
NH OH NH
NH
base than 2 O, and this is really equivalent to what we have been accustomed to say with respect to the small 4 4 +, that H 2 O is less ionized than hydrolysis of
NH
NH OH
to form
11.
OH".
is
1 a complete terminology for this system of which the following definitions are samples.
There
AMPHIPROTIC SUBSTANCE
as an acid or as a base.
a substance which can act either

:
Example HCOa~.
Cf. Journal of Chemical Education, Vol. 16, page 535 (1939).
404
Ch. XXII
APROTIC SOLVENT
C<jH0.
a solvent which will neither lose a proton
to the solute, nor gain a proton from the solute.
Example:
LYOLYSIS or Solvolysis (also Hydrolysis, Ammonolysis, and so forth) a protolytic reaction between a cation acid or an anion base and the solvent (water, ammonia, and so + forth). Example: NH 4 + H 2 O *=* NH 3 + H 3 O+;
CN" + H 2 O
MONOPROTIC ACID
<=*
HCN +
OPT.
an acid which has only one proton to a base. Examples: HC1; HS0 4 ~. Also Diprotic Acid, to lose
etc.,
and Polyprotic Acid. PROTOLYSIS, PROTOLYTIC REACTION a reaction in which a proton is transferred from an acid to a base. Example: A! + B 2 -> A 2 + Bi; as in HC1 + CH 3 COO~ -> CH 3 COOH
cr.
SALT
12.
an
ionic
compound. Example: NaCl.

is
The
and
chief
advantage of this system
that
it
ascribes
basic strength to the substance itself, and not to acidic its behavior in a particular solvent. This is particularly helpful to the organic chemist, who finds it necessary to change
from one to another of his ordinary solvents, such as ether, alcohol, benzene, toluene, or mixtures of them. All experienced chemists would agree, for example, that acid strength de-
HC10 4 HC1, CH 3 COOH, 2 O, regardand, similarly, that basic strength decreases in the order Ba(OH) 2 2 O. 3 13. The order given in Table 1 would doubtless be regarded as a completely satisfactory representation of the relative strengths of these species as acids and bases, divorced from the specific influences of solvents by referring each conjugate
creases in the order
less of solvent
, ,
NH H
,
pair to unsolvated proton.

is
The effect of a particular solvent then introduced by considering its own reaction with the proton. To illustrate, let us compare the results of dissolving
(a) water, and (6) liquid ammonia. stronger base and the latter a much stronger base than Cl", hence, while both react with HC1,
HC1 gas in an excess of The former is a slightly
15
ACID-BASE SYSTEMS
405
as follows:
(a)
(b)
HC1
(gas)
(gas)
HC1
(b)
+H + NH
2
(liquid, excess)
3
= H3
O + CT.
4
(liquid, excess)
NH + +
CT.
proceeds much farther than (a) as shown by the fact that HC1 gas escapes from concentrated HCl(aq.) but not from equally concentrated 4 C1 in liquid 3
Reaction
NH
NH
But
on the
in spite of the fact that the effects of different solvents
are adequately accounted for in this way, it should be realized that the equilibria in Tables 1 and 2 are still not
H+
independent of the nature of the solvent, because the forces acting upon the acids and bases themselves are different in
different solvents.
set of equilibrium constants derived
from aqueous solutions could not be applied unchanged to
same species in alcohol, ether, or benzene. users of the system must be content with approximate solvent is not predictions only when changing solvents.
solutions of the
The
simply space in which molecules are free to as they do in the gaseous state.
14.
wander unaffected
The substances
listed in
Table
are chiefly those used
aqueous solutions, selected so as to set forth the new point of view in terms of species whose behavior is already " familiar in the water system." The proton-donor-acceptor
in
system
is
chiefly valuable, however, in organic chemistry,
and therefore a tabulation consisting mainly of typical organic acids and bases as in Table 3, should prove more useful. The arrangement brings out certain general rules
familiar to organic chemists, such as that acid strength is for increased by substituting 5 for 3 C6 3 Cl for
CH
CH
H,
C 6 H6
for
H,
CH3
for
C2 H 5
15. The Electron-Donor-Acceptor System. While the acidbase system described in the paragraphs immediately prececling escapes from the restriction of OH~ as the criterion of basic character, it limits the definition of acids to substances capable of splitting off protons, as illustrated by the lists in Tables 1 and 3. Now there is still another point
406
Ch. XXII
of view, one which escapes this restriction also, and which
has proven its value for over a century, particularly in interpreting combinations between oxides. Berzelius, long before the discovery of electrons and protons, explained combinaCO2 as due to attraction between tions such as CaO
TABLE
Relative Strengths of Organic Acids
and Bases
Bases
Acids
HC1
H 8O+ CH 3OH 2+ C2H OH 2+

6
= = = = =
= = = = = = = =
H+ + CF H+ + H 2 O H+ + CH 3OH Methanol H+ + C 2 H OH Ethyl

5
alcohol
(CH 8) 2OH+
(C 6 H 6) 2 NH 2 +
H+ + (CH 3
)2
Dimethyl
ether
H++(C H
6
6) 2
NH
C 6 H NH 3+ C1CH 2 COOH
5
CHsCOOH
C 6 H 6 COOH
Chloroacetic acid Acetic acid Benzoic acid
NH +
4
C 6 H 5OH
Phenol
CH 3 NH 3+
H+ + H+ + H+ + H+ + H+ + H+ + H+ +
H+ H+ H+
C 6 H NH 2 Aniline C1CH 2 COO~ CH 3 COO~ C 6 H 6 COO"

5
Diphenyl amine
NH
3
8
C 6 H O~
CH 3 NH 2
3
Methyl amine
H 2O CH OH
3
Methanol
NH
and
= = =
+ OH~ + CH CT ~ + NH
2
parts of molecules, and regarded oxygen, the "acidgenerator," rather than hydrogen as responsible for acid
character. It
was recognized that there
is
no great distinction
between two such reactions as
Ca(OH) 2
+H CaO +
SO3 = CaSO3 SO2 = CaS03
+ H2 O and
.
oxide and
but natural, therefore, to designate CaO as a basic SO2 as an acid oxide. Again, since H 2 O, CO2 SO2 and SO3 are evolved with increasing difficulty in that order from their solid compounds with CaO, it is consistent to
It is
, ,
explain this as due to their increasing acidity.
The
relative
T<5
ACID-BASE SYSTEMS
407
basic characters of MgO, CaO, and BaO can be inferred as increasing in that order from the decomposition temperatures of their combinations with any one of the relatively
It is thus possible to arrange acid oxides, 2 O, CO 2 or SO 2 the following series of oxides, from the most basic to the
,
most
acid, in
such a
way
are in the series, the
more
2
that the farther apart two of stable is their combination.
them
Most
basic
K O, Na O,
2
BaO, CaO, MgO, ZnO, CuO, H 2 O, CO2 SO 2 SO3 Most FeO,

,
acidic
The increase in stability as oxides farther apart in the list
compounds
is
are chosen from
illustrated in
Table
4.
TABLE 4
Decomposition Temperatures of Hydroxides and Carbonates
HO
2
CuO <100
MgO
184 553
CaO
547 897
BaO
988
1361
C02
The
series is a perfectly
fact that
H+
is
good acid-base series in spite of the nowhere involved. Similar compounds are
formed between halides, as illustrated by
KA1C1 4 = KC1
A1C1 8
PtCl 6
PtCl 4
2 KC1,
K SnCl
2
- SnCl 4
2 KC1.
16.
Another characteristic of acid-base reaction, the color

Pyridine,
changes of indicators, can also occur in systems from which
H+ is absent.
H
C
/
HC
II
CH
I
HC
\
CH
//
and triethylamine,
N (C 2 H 5 3 N can
)
act as bases, and SOj,
408
PR/NC/PLES OF CHEMISTRY
,
Oi. XXII
BC18 and SnCl* as acids in CC1 4 or dioxane,
O
/
\
HC
II
CH
II
HC
\
CH
/
O
giving color changes with suitable indicators on neutralization like ordinary acids and bases. It is therefore an exaggeration
o claim that
reason
cases
is
H+
it
is
the crux of acid-base neutralization.
The
why
that
it is
responsible for acid character in so many is an "electron acceptor" in the sense that it
can unite with unoccupied electron pairs of other ions or molecules in rapidly reversible equilibrium, as illustrated by cases 1, 2, 3, in Table 5. But SO 3 and A1C1 3 in cases 4, S, and 6, are also acceptors, and can behave as acids towards
,
and CP. KC1, due to their ions, O is an acceptor on account of the ability of its hydrogen to form "hydrogen bonds" (cf. Chapter XX, paragraph 12) between the atoms N, O, and F. Ag+ is an acceptor to NH 3 due to its ability to form two more or less covalent bonds. Case 9, pyridine and BC1 3 is a neutralization reaction that is quite "aprotic," which can be carried out in an "aprotic" solvent, with an indicator to mark the end
the bases, In case 7,
CaO and
H2 O
point.
It
cases, notably 5
must be admitted however that in several of the above and 6, the new bonds formed are doubtless
has been "accepted" is a negative ion, O or Cl", rather than an electron pair. Indeed, there are all gradations from one to the other, and it would seem absurd to define acid-base reactions in such a way as to require an arbitrary line to be drawn somewhere 3 along this somewhat hazy way. Again, the union of and H2 O, case 7, is now believed to be due to their strong dipoles and closeness of their approach rather than to the formation of two covalent bonds by hydrogen. That fact
ionic rather than covalent.
What
NH
18
ACID-BASE SYSTEMS
409
should not, however, exclude this reaction from the category of acid-base reaction, where it certainly belongs from the are thus led point of view of actual chemical behavior.
We
back to the all-inclusive view of chemical union, held a century and a half ago by such master minds as Lavoisier and Berzelius, that the positive part of one molecule is attracted to the negative part of another with a strength depending on the difference in electric character, and we need not differentiate between the several sources of this difference, whether ionic charge, permanent dipoles, or
unoccupied electron pairs. 17. The donor-acceptor concept of acid-base reactions must not be confused with the electron transfers involved in oxidation-reduction reactions. The former consists in a
unequal sharing, the latter in a complete transfer. The distinction may be illustrated by comparing the reduction of SO 3 to SO 3 by acquiring the electrons of Ca with the neutralization of S03 by addition of O from CaO to form SO 4
less
.
more or
:0
SO
as oxidizing agent
Ca
(:)
>S
:O
:0
SO 3
as acid
Ca ( 6
:
..
) /
>S
:O
18. Relative Values of the Different Systems. There is a temptation, when dealing with rival points of view, such as these systems of acids and bases, to assume that one of " them is "right" and the others wrong/' forgetting that they are only convenient, altogether artificial schemes for classifying reactions. No one of them is either true or false. The distinctions between them are not at all like the difference between the phlogiston theory of combustion and the
"oxygen theory
(cf.
Chapter
I,
paragraph 19). The choice
H
:0:
[ij
:o
:
:eo
:
:Q:
:
:Q :^ :Q
:
:o
O
c*
W
W
O'-W'O:
:rt::
*
l
i
11
410
hp^
w ^ 55
"
:
. >_,
CD
W
M
O W M
:
n ^ w
:
:
i
Wo
W
Cvl
Wei
H O
PQ
H^
1
O e i
oo
411
412
PRINCIPLES OP CHEMISTRY
Ch. XXII
between them should depend solely upon the region of chemistry in which one is operating, like the choice between the different clefs in music for recording the part for a particular instrument. Violin parts are usually written in the
treble clef, viola parts in the alto clef, and violoncello parts in the bass clef because these best correspond to the ranges
of the respective instruments, not because it would be either wrong or impossible to write a given part in another clef.
Just as a trained musician can read from any clef, so an intelligent chemist can select whichever system of acids and
bases best suits his particular purpose.
is
perfectly adapted system to reactions in that solvent; the proton system is preferable to the preceding ones for dealing with the variety of solvents and bases encountered in organic chemistry, but it is inadequate for dealing with the cases continually coming to light, even in organic chemistry, of acid behavior in the absence of H+. A particularly striking case is offered by the substitution of BF3 for H 2 SO 4 as an acid catalyst in the production of high octane gasoline. And the mineral chemist is scarcely likely to agree to definitions which would deny him the right to refer to an igneous rock as acidic or basic. It is desirable that the chemist retain sufficient elasticity of mind to avoid definitions which are so rigid as to act as shackles rather than serve as tools.
to
The "water system" aqueous solutions; the ammonia
CHAPTER
XXIII
STRUCTURES OF INORGANIC
1.
COMPOUNDS
Crystal Structures. When a narrow beam of X-rays passes through a crystal onto a photographic plate, a diffraction pattern of spots (cf. Chapter II, paragraph 13) is obtained whose arrangement depends upon the arrangement of atoms or ions in the crystal lattice.
A
Fig.
sample
1.
pattern
is
illustrated
in
The type and dimensions
of the
X-ray pattern usually serves to identify the type of lattice and to permit the
calculation of the interatomic distances.
Errors of identification are sometimes made in the case of complicated crystal

lattices.
2.
The
upon
crystal their axes of
1 systems are based symmetry, shown in
Fig. 1. Typical X-ray diffraction pattern.
Fig. 2. Additional faces usually appear, and some faces generally outgrow others, distorting ideal shapes of the crystals.
The relative lengths them are as follows:
of these axes
and the angles between

Mono-
Cubic
Tetragonal
Triclinic
Rhombic
clinic
Hexagonal
3 equal
Relative length of axes
None
3 equal
all
2 equal
all
equal
Angles between
axes
3. Lattices.
90.
90.
all
None
90.
2 at 90.
90.
and
at 90.
120.
Different kinds of lattices
may conform
,
to
a single system, thus the cubic system includes the following:

1 Cf. Latimer and Hildebrand, Reference Book of Inorganic _ Chemistry York, The Macmillan Company, 1952, Appendix V.
New
413
414
Lattice
Examples
CsCl,
Li,
Ch. XXIII
Simple cubic Body-centered Face-centered
NH
4 C1,
FeS 2
Na, K, Cr, a-Fe, Al, Ca, Cu, NaCl, KCl, MgO, PbS,
Si,
Fig. 3 Fig. 4
CaF2
Fig. 5
Diamond
4.
Ge, Sn (grey)
Fig. 8
Close Packing. In the case of elements, whose atoms alike, there are two arrangements which represent the closest possible packing, the face-centered cubic (Fig. 5) and the hexagonal (Fig. 6). Both of these may be considered
are
all
Cubic
Rhombic
Monoctfaic
Triclinic
Hexagonal
Fig. 2.
Crystal systems.
as built
all
up of close-packed layers (shown in Fig. 7) where the spheres are in contact, making triangular and hex-
agonal patterns in which every sphere is surrounded by six others. A second identical layer is placed on top of this
first
one,
its
spheres in the first.
spheres fitting into pockets formed by three A third close-packed layer is next placed
on top of the second in the same way, but there are two sets of pockets in which to place it: one in which each sphere
INORGANIC COMPOUNDS
in the third layer is directly
415
over a sphere in the first, forming the hexagonal close-packed lattice (Fig. 6); the other in which the spheres in the third layer are over holes in the
first,
forming the face-centered cubic close-packed
lattice
Fig. 3.
Cesium iodide
lattice,
simple cubic.
The
ions, radius 2.16
Angstr0ms; the small ones, cesium
large spheres represent iodide ions, radius 1.69 Angstr0ms
(Fig. 5), where only one ball of the third layer has been placed in position in order better to reveal the cubic faces containing one at the four corners and one in the center of
Fig. 4. Body-centered cubic

lattice.
Fig. 5.
Face-centered cubic
lattice.
each.
The elements
of a hexagonal prism are clearly seen
in Fig. 6, where the hexagonal arrangement occurs only in the horizontal plane. In the face-centered cubic lattice, the
416
Ch. XXIII
hexagonal arrangement is found in each plane cutting the diagonals of the cube. It is obvious that these two lattices have the same density,
since there
is
no difference
in the relation of
adjacent close-
packed
5.
layers.
It is interesting to
properties of iron and steel caused
note that the changes in the physical by rapid versus slow

cooling (annealing) are connected with the change between the body-
centered and face-centered structures. Also, the presence in Fe of Ni, naturally face centered, stabilizes that
Fig. 6.
Hexagonal closepacked lattice.
Fig. 7.
Close-packed layer.
structure, permitting the necessarily slow cooling of large masses of nickel-steel armor plate without the loss of "temper."
Fig. 8, the atomic arrangement is less but is such that each carbon atom can attach itself by an electron pair to its 4 nearest neighbors. The 4 chemical bonds of carbon are thus all called into play, and since the carbon atoms are very small, and can get very close together, so that the forces between them are very
6.
In diamond,
easily described,
large,
is
diamond
is
the hardest of
all
known
substances. It
possible to see in the
diamond
lattice the
main structures
of organic chemistry, viz., the tetrahedron, the zigzag chain, and the hexagon. The lattice of graphite, shown in Fig. 9, retains the chain and the hexagon, now flat, but has lost
the tetrahedron. The flat planes are far apart and can slide over each other; hence graphite is a lubricant, in striking contrast to diamond. It is also an electric conductor, due
INORGANIC COMPOUNDS
to the loosening of the electrons between the planes,
is
411
and
much
less
dense than diamond.
In the crystal of an un-ionized substance, such as benzene, the molecules do not lose their identity, so that the same molecule which builds up a crystal comes off when the crystal
Fig. 8.
Diamond
lattice.
This lattice exhibits various arrangements of carbon

tetra-
atoms found in saturated hydrocarbons: the zig-zag "straight chain," the hedron, and the hexagon.
dissolves or evaporates,
unlike the
NaCl
crystal,
off
where a
sodium ion, in leaving the surface, might go one of the surrounding chloride ions.
with any
7. The equal spacing of the ions in crystals of the NaCl type offers the strongest kind of evidence that there are no permanent molecules of NaCl present. Each Na+ is surrounded at equal distances by 6 Cl" and vice versa. Similarly, in a crystal of calcite, CaCO 3 the lattice (shown in Fig. 10)
,
is
made up
of the ions
all
Ca++ and
CO3
Moreover, the
C
a
O
flat
distances are
the same, showing that the
CO3
is
418
Ch. XXIII
Fig. 9. Graphite lattice. Here the chains and hexagons remain, but layers of the latter are separated from each other so much that they can slip past each other and the electrons are loosely held; hence while diamond is the hardest of all substances and an electric insulator, graphite is a lubricant and a conductor.
triangle and that there is no justification for regarding the Ca as bonded to O-atoms, as implied by the formula
O
\
Ca
\
C=O
O
of
that used to appear in textbooks. Similarly, the structure 4 C1 shows it to be made up of the ions, (NH 4 )+CL~,
NH
and that there
no basis for assuming pentavalent nitrogen, as used to be done before the various types of valence (cf. Chapter IX) were clearly distinguished.
is
INORGANIC COMPOUNDS
41'
Fig. 10.
Lattice of
CaCO and NaNO8

3
8.
It is found, in general, that the

, ,
polyatomic
Cu(NH 3 ) 4 ^, Cr(NH 3 )a^ ClO-f Fc(CN) 6 are quite symmetrical in their crystals. This leaves open, however, the question whether the surrounding atoms or groups are bound to the central atom by electron-pair bonds or only by electrostatic attraction. Thus, S0 4 may be
as SO*",
represented either by
ions, such 4
:O
O""
:
:
or by
c
420
Ch. XXIII
and the electrons may "resonate" between the two configura(cf. Chapter XVIII, paragraphs 9 and 23) so that we ascribe to the bond a certain percentage of each charmay acter. It is possible to distinguish them in cases where there is a difference in magnetic moment, due to unpaired and FeFe have very different electrons. Thus Fe(CN) 6 moments, indicating that the former is largely magnetic covalent, the latter completely ionic. Covalent bonds are apparently rather general with N0 2 CN, and CO complexes.
tions
,
negativity scale given in Chapter V, paragraph 14, repeated and extended here in Table 1 for convenience, may
serve as a guide to indicate the degree of ionic character a bond is likely to possess.
TABLE
i
The
Electronegotivity Scale (after Pauling)
K
Na
Ba Ca
9.
0.8
0.9 0.9
1.0
Li
1.0
1.2
1.5
Ti
1.6 1.8 1.8
B
As
2.0 2.0
2.1
2.4
Br
2.8
Mg
Be
Al
Sn
Si
Se
2.4
2.5 2.5
H
P
C
S
N O
F
3.0
3.5
1.5
Sb
1.8
2.1
4.0
The
arranged be due in part to the relative sizes of the atoms and in part to the preferred directions of the electronic orbitals.
in
four surrounding atoms, ions, or groups may be a plane square or tetrahedrally. The difference
may
The
following are examples of the two types

Square grouping
Tetrahedral grouping
Ni(CN) 4
Si0 4
PtCU" PdCU"
cuci 2 (H 2 o)2
P0 4 SO4 cior
"
Ni(CO) 4
Tetrahalides
CH
10.
,
NH +
4
coordination
number
of five, as in
;
Fe(CO) 5 and
, ,
trigonal bipyramid one of six to an octagon, examples of which include Fe(CN) 6 Fe(CN) 6 Co(NH 3 ) 6+++ , PtCl 6 , SF 6 . The latter structure allows
,
PC1 5 corresponds to a
13
INORGANIC COMPOUNDS
when two
,
421
isomers
Co(NH 3 )4(NO 2 )2 + where
different substituents are present,
as in
either
the
two NO2 groups may be
adjacent or opposite. 11. The tetrahedral structure of
CH* and NH*4
"
cannot
be verified by
rays because the hydrogen atom does not scatter sufficiently to reveal its position in any of its compounds. We must rely upon such evidence as is furnished by
the
absorption spectra, which show that vibration are those of a tetrahedron.

TABLE 2
their
modes
of
Bond Angles and Dipole Moments

D Bond
, ,
angles
19 Dipole moments X 10 electronic units
180 180 180
0.116
1.85
1.1
104 27' 92 16' 119 32'

127
1.7
0.5
140
100
111
15
0.3
?
1.7
12.
Gaseous Molecules.
Triatomic
molecules
are
may
be
either linear or bent.
The bent molecules
due to the tendency of the electron pairs of to approach a tetrahedral arrangement except as distorted by the end molecules. Table 2 gives bond angles for triatomic molecules, calculated from vibrations of the molecules as revealed by spectroscopic data or from the interatomic distances determined by the diffractions of electrons, which have an associated wave length and can serve for this purpose with gaseous molecules where X-ray diffraction is not sufficiently intense. The bond angle for a regular tetrahedron is
109
28'.
most numerous the middle atom
13.
The
dipole
moments
to distinguish bent and
furnish additional evidence serving linear structures. If, for example,
422
Ch. XXIII
were linear, H O H, it would not have a dipole moment, and C0 2 cannot be unsymmetrical, for then it would
H2O
CO group has one. have a moment since the 14. In view of the natural tendency of bonds to approach
tetrahedral angles, we find linear triatomic molecules only = C = O, where double or triple bonds are formed, as in
indeed, linear molecules are strong evidence of multiple bonds. They are largely limited to the first row elements, C, N, 0.
Polyatomic Molecules. The molecules of active phosphorus, P 4 and arsenic, As 4 have the 4 atoms at the corners
15.
, ,
of a regular tetrahedron. The angles halides of P, As, and Sb, are all close to
in the tri-
to be flat pyramids. This is which show them to be unsymmetrical
100, showing them confirmed by dipole moments,

(cf.
Chapter
.V,
Table
6).
APPENDIX
SAMPLE FINAL EXAMINATION QUESTIONS

FOR THE
1.
FIRST
SEMESTER
Which
(a)
(b)
(c)
solution in the following
list:
0.01
0.5
Af-HCl
2
3
(/)
0.001
0.01
0.1
M-KOH
4) 2
3
M-Na CO
(g)
0.001 M-Ba(OH) 2 3 (d) 0.01 (e) 0.01 Jf-NaCl
(h)
(i)
M-(NH SO 4 M-NaHCO
lf-H 2 SO 4 Jkf-NaOH
(indicate
M-NH
0.01
0.5
(j)
has a molal concentration of

the corresponding letter) 2 8 (4) 10(1) 1010~ 3 10- 6 (2) (5) 11 7 (3) 10(6) 102.
OH~ nearest to
(7)
by writing
10~ 13
The atoms R, X, Y, and Z have, respectively, one, two, two, and seven valence electrons. Their atomic numbers increase in the and R have 8 electrons immediately order, X, Y, Z, R. Atoms below their valence electrons and atoms Y and Z have 18. Which Write the formula of are atoms of metallic elements? of the complex of the simplest ion of Z
ammonia
that
3. 0.2
is
ion most likely to form the strongest base
of the hydroxide
between
X and
of
of a probable
compound
Z
3
,
4.
grams; will give weighs moles of CO 2 gas. This gas will occupy liters at 273 C. and 0.2 atmosphere. The BaO left on strongly heating the 0.2 mole of BaCO 3 will react with 5 liters molal or normal Ba(OH) 2 of water to give The concentration of OH" in this solution will be cc. of molal. 100 cc. of this solution will neutralize 0.5 Af-HCl. + shows the If the reactions: ion,
grams, or
.
mole
BaCO
hypothetical
2
following
(a)
MCI + Na CO
easily dissolves in
(b)
HNO
(aq.) gives
3
a ppt. which, after
filtration,
(aq.).
(aq.).
M SO
2
dissolves in
KCN
423
424
(c)
APPENDIX
M S0
2
ppt.
+ H S gives M
2
(d)
The product obtained on

and
filtering
(aq.) State, in
out
is
ppt. treating insoluble in

2
M SO
2
with
Na CO 3
2
HNO
(aq.).
words, two reactions that you can predict with certainty from these observations.
5.
State the effect, quantitatively where you can, of each of the following changes upon (a) the number of molecular impacts per second per square centimeter upon the containing walls and (b) the force of each impact. (1) Gas in a cylinder with a movable piston, immersed in a
large water bath,
is
compressed from 3
(6)
liters to 2 liters.
Ans.
(2)
(a)
The air pressure in an automobile tire is slowly pumped from 25 Ibs. per sq. in. to 30 Ibs. per sq. in. up Ans. (a) (b) (3) H 2 S gas is kept in a closed vessel at constant temperature until it has all decomposed into H 2 and liquid sulfur. Ans. (a) (b)
6.
Which
of the substances,
'
CaSO 4 CaSO 4
(a)
(b)
(c)
H O, K SO ZnS, ZnSO Na B O CaCl CaSO H O, MgO, (NH SO is most appropriate for each
2
2
4, 4,
NaOH,
4
,
A1 2O 3
A1 2 (SO 4 )3,
4
7
,
Na CO
2
3
4
>
2,
4) 2
of the following uses:
Water softener White paint

Abrasive
(e)
Cleaning metals for welding or hard soldering
(/)
Making
plaster casts
(d)
Making soap from
fat
(g) Fertilizer
(k) 7.
Avoiding dust on roads ....

remaining after evaporating
Give the formulas of the

(a) 0.1
(b)
(c)
solids
to dryness solutions of the following:
0.02 mole 0.02 mole
(d)
(e)
mole AgCl and 1 mole HNO 3 NH 4 C1 and 0.05 mole of NaOH Zn(NO 3 ) 2 and 1 mole HC1 0.1 mole Zn(NO 3 ) 2 and 0.01 mole H 2 SO 4 0.02 mole CuSO 4 and 0.2 mole HNO 3
8*
Given that the elements A, B, C, D, and E have atomic numbers (nuclear charges) of 6, 9, 13, 19, and 30 respectively, underline
correct answers below, (a) The compound of
(Jb)
and B will have the formula AB, B, AB 4 A 4 B. Which of the following complex ions are stable? C(NH 3 ) 4++ ? D(NH 8) 2+, E(NH 3) 6+++, E(NH S) 4++ .
AB A
2,
QUESTIONS FOR
(c)
FIRST
SEMESTER
425
Which
of the elements are ordinarily gases with diatomic molecules? A, B, C, D, E.
The compound of B and will be essentially ionic, electron pair bonded. (e) Which of the elements are metals? A, B, C, D, E. (/) The compound of B and C will have the formula CB, CB 2
(d)
,
CB 3 CB 4 C 4 B,
, ,
026.
list:
9.
Which
(a) 0.1
(b) 1
(c) 0.5
solution in the following
M-HAc
M-Na 2 CO 3
(d) 0.05
(e) 1
(f) 0.1
Jlf-NaAc
Af-Ba(OH) 2 Jtf-NaOH
(g) 1
Jlf-NH^c
(*) 1
M-HC1
by
M-HC1
has a molal concentration of
OH~
nearest to
(indicate
writing the corresponding letter) 7 5 (c) 10- ..................... (a) 10- ................ 10~ u .................... 10- 1 ................ (d) (b)
10.
Underline the formula of that substance in each of the following groups which has the property stated in the highest degree
:
(a) Solubility in
(6)
(c)
water:
gases):
CaCO
3,
BaSO 4 CaSO 4 CaC 2O4

,
Density Cone, of
(all
O,
H NH C H
2,
3,
OH":
0.5
^-Na 2 CO
0.05
0.05
M-NaHCOs, M-Ba(OH) 2 1 Jlf-NH 4 3,
OH,
(d)
M-KOH
,
Cone, of H+:
0.01
Af-H 2 SO 4
4
3,
M-HAc,
M-NH N0
(e) (f)
0.04 Jlf-HCl
Atomic number:
Acidic nature:
K, Mg, Al,
Zn(OH) 2
Li, Ag, Cu Cu(OH) 2 Ca(OH) 2

,
LiOH
(g)
Degree of hydrolysis:
0.1
Af-KAc,
0.1
M-NH4Ac,
0.1
(h) Effect
on the freezing
1 liter
point of
(i)
of water:
0.02 mole of KC1, 0.01 mole of 2 SO 4 0.03 mole of HAc, 0.01
Ionizing potential of the
mole of BaCl 2 Na, Ca, Al, Ag
gaseous atom:
0')
Insolubility in water:
CaSO 4 Ca(OH) 2 CaC 2O 4 Ca(N0 8 ) 2

,
11.
Some solid Ca(OH) 2 is in equilibrium with its saturated solution. How will the amount of solid Ca(OH) 2 be affected (indicate for increase, decrease or practically or by writing +, no effect, respectively) by adding small amounts of the
following:
426
(a)
(b)
APPENDIX
KOH
(d)
(e)
Ca(NO 3 ) 2 (c)NH 4 Cl
HAc CaCO 3
(g)
(NH 4 ) 2 C O 4
2
(/)
KN0
(k)
ZnSO 4
12.
Give the concentration of OH~" in each of the following solutions as accurately as you can. Some latitude will be allowed in
certain cases:
(a) 1
(ft)
Jkf-NH 4OH
0.1
0,01
M-NH OH
4
M-Ba(OH) 2 and
Af-HCl
of
100
the
cc. of 0.05
(h)
(c) 0.5
Af-Na 2 C0 3
molal
solution
(d) 0.01
(e)
(/)
(g) A
Jlf-NH^c CO 2 at 1 atm Saturated Ca(OH) 2

solution
sodium salt of an acid whose degree of dissocia.
..
tion
is
0.01
of
that of
from mixing 100
resulting cc. of
HAc when
both are in
molal solution
13. The following are mixed in 1 liter of water in the order given. Write the formula of the precipitate finally present. 0.05 mole of CaCl 2 1 mole of HC1, 0.1 mole of Na 2 SO 4 0.1 mole of 3
, ,
NH
0.2
mole of
Na 2 CO
3.
SAMPLE FINAL EXAMINATION QUESTIONS FOR THE SECOND SEMESTER

Questions 1-4 represent hypothetical
"unknowns," made by
selecting one or more of the substances listed in each case. The amounts are not necessarily equivalent but are always more than
mere
traces.
the basis of the observations given, write, in the space imfor each substance known to mediately following the formula, for each substance known to be absent, and a question be present, mark (?) for each substance whose presence is in doubt.
On
1.
Pb(NO 3)2 CuSO 4

HgCl 2
ZnCl 2
Treatment with hot water gives a white residue and a colorless

solution, which, after filtration,
K
2.
(NH 4 ) 2 SO 4
2
gives a white ppt. on addition of ammonia, insoluble in excess.
CrO 4
3
NaN0
Zn
Treatment
Cu Ag
with 0.1 Jl/-H 2 SO 4 gives effervescence, and leaves

a residue, which, after separa-
QUESTIONS FOR SECOND SEMESTER

Fe
Al
tion from solves in 2
427
dis-
the
solution,
M-HNOs
to give a
sulfuric
colorless solution.
The
acid solution gives no ppt. on addition of 2 S but a black ppt. upon subsequent addition of
NaOH.
3.
SnCl 2 Fe 2 (S0 4 ) 3
KHSO
Cr 2 O 7 ..
2
Hg
Cl 2 ...
.
FeS0 4 ...
Ba(N0 3 ) 2
ZnCl 2 ....
4.
........... .......... ........... ........... ........... ........... .......... ...........
Treatment with water gives a green solution and leaves a white residue, which is filtered out. The green solution, upon
addition
of
Af-NaOH,
gives
a ppt., soluble in excess. The white residue is not visibly

affected
by ammonia.
PbCU....
SnCl 2
.
..
.
ZnSO 4
Cr 2 O 7 Fe 2 (S0 4 ) 3
2
.
PbO
........... ........... .......... .......... ...........
Treated with hot, 2 M-HC1, the unknown gives a gas with a

sharp, suffocating odor, a greenish solution and no residue. After neutralizing part of the HC1 and passing in 2S, there is
a deep yellow ppt., which

filtered out.
is
green and after adding an excess of 6 M-NaOH there results a green

ppt.
5.
The
filtrate is
and a green
solution.
Answer the following by underlining the symbol or formula of the substance having the characteristic called for:
(a)
highest melting point (b) The greatest hardness (c) The greatest affinity for electrons (d) The largest number of valence electrons (e) The highest oxidation
(/)
The
Fe, Zn,
W,
,
Ni, Bi
SnO 2 SiO 2 PbO 2 SO 2 C1 2 Fe+++, H+, I 2 Zn

,
Sb, Sn, Si, Al,
Ag
3,
VO++,
number of vanadium The largest degree of

hydrolysis
NH VQ V ---4
,
(S0 4)3,
8,
VS 2
V(CN) 6
KAsO 8 KP0 KAsO 2

B, Br, Ba, Bi
3,
KN0 KN0
2,
(g)
The largest atomic number
428
(k)
APPENDIX
The
in
largest
solubility
HgS, CuS, FeS, PbS, SnS
water
6.
State the colors of the following:

(a)
(fr)
Fe 2O 8 Cr 2 8
A1 2O 8
(0
(g)
HgS
(c)
(*)
(*)
(d)
(e)
Pb 8O 4 PbCr0 4
Cr 2 7 Fe++ Fe+++
C1 2
"
(*) I,
(/)
vapor
.
Cu++ (m) Fe 2 Fe(CN) 6

(n)
(o)
PbO 2
CoSiO 3
(j)
7.
Underline the two substances in each of the following series which most closely resemble each other in chemical behavior: SiO 4 (a) A1+++, Bi+++, Cr+++, Fe+++ (d) SO 4 L C1O 4~,
(b)
(c)
BaO 2 SO 2 MnO 2 Pb0 2 K+ Ag+, H g2 ++, Cu++

,
,
CrO 4
(e)
HgS, PbS, FeS, ZnS
8.
Answer the following by underlining the substance having the

characteristic called for:
The The The
greatest hardness greatest affinity for electrons

largest
MgO, As 2Oa, Al 2Oa, CaO Ag+, Hg++, C1 2 Br 2 Fe+++

, ,
number
of
Br, B, Ba, Bi,
Be
valence electrons
The highest atomic number The lowest oxidation number of molybdenum The largest atomic radius The lowest melting point The strongest reducing
power
9.
Ag, Hg, Mg,

,
Mn, Al
,
Na 2 MoO 4 MoFe, MoaOs, Mo(OH) 3

,
MoS 2 MoO
Na, Cr, Ca, K, Br

C,
I",
Si,
Ni, Fe, Sn F~, Cl~, Br~
An
As
electric cell consists of
silver chloride,
an electrode of silver coated with and another of zinc, both immersed in a solution
.
of 0.01
M-ZnCl 2
the cell discharges, electrons flow in the external circuit from the electrode. The oxidizing agent is and the reducing agent is The half-reaction occurring at the silver-silver chloride electrode is If the concentration of the ZnCl 2 were increased the electromotive force of the cell would be The cell evolves heat while discharging, hence the electromotive force would be by lowering the temperature.
10.
How many moles of each of the following oxidizing agents would
be required to oxidize 0.1 mole of TI+++ to TiO++ and how

+ would be used moles of (denote by (denote by +), in each case. Fe+++ C1 2 Oxidizing agent Hg++
429
many
),
or liberated
MnO
"
4
to
Mn++
No. of moles No. of moles of

11.
H+
in that
8, 8, 2
The atoms X, Y, and Z have atomic weights

order.
X has 2,
of
of
number number
is
Y
Z
increasing electrons outside its nucleus. The is 11 greater than that of and the is IS greater than that of X. The simplest
atomic atomic
ions of
these elements are
The
strongest reducing agent
The
least metallic
element
is
Questions 12-15 represent "unknowns" made by selecting one or more of the substances listed in each case. The amounts are not necessarily equivalent but are always more than mere traces. Mark for those known to be present, for those known to be absent, and ? for those which are undetermined.
12.
KHSO4
Pb(NO 3 )2 NaNOa (NH 4 ) 2 Cr0 4 BaCOa
KC1
The unknown
dissolves in water
to give a clear orange-colored solution.
13.
AgNOa
Hg2Cl2
The unknown
is
partially sol-
KNOs
NH
C1
uble in water, but leaves a white residue. When the residue is treated with 4OH, a solution
NH
Na 2SO 4 HgCU
and a black residue are obtained. Acidifying the ammoniacal solution with 1 Jkf-HNOa gives a
The gradual addition of NaOH solution to the original aqueous solution gives a white precipitate insoluble in excess NaOH solution.
white precipitate.
14.
FeS Cr(OH) 3
The unknown
is
partially sol-
BaCO 3
NaCl
uble in cold water. When the residue is treated with 6 MNaOH, a green solution is obtained, and a dark residue which dissolves in 1 M-HCl with effervescence. The addition of
KNO NH C1
3
NaAc and Na2CrO4
solution
430
APPENDIX
to the boiled
HC1
solution gives
a yellow precipitate. The original aqueous solution imparts a violet color to the flame which can be seen without the use of a cobalt
glass. The addition to this solution gave
of
NaOH
no odor.
15.
What
\c)
is
HgNH
,
the color of (a) SnS 2 Cl (<*) Fe 2 Fe(CN) 6
(b)
(e)
PbCrO 4
Fe(OH) 3
(d) 6
16.
Which solvent in the following list: (c) 6 AT-NH 4OH, (6)Cl 2 (aq.), (a)CS 2
(e) 0.3 Jlf-HCl,
(/) 0.3
#-H 2SO 4
(g)
NH SH(aq.)
4
M-NaOH,
by
,.
would be most
(a)
(6)
(c)
effective in dissolving (answer each simply writing in the corresponding letter from the above list)
PbSO 4
AgCl
(e)
(/)
BaCrO 4 CaC 2 4
SnS 2
Hg 2 Cl 2 (d) Sulfur
17.
(g)
(A)
CuHAsO 3
The
following reactions are observed, using 0.1 molal solutions
and approximately equivalent amounts: UO a++ + 4 H+ + Sn++ = Sn++++ + U++++ + 2 H 2O Cd + 2 TiO++ + 4 H+= Cd++ + 2 Ti+++ + 2 H 2O 2 Ti++ + Sn++++ = 2 Ti+++ + Sn++ + Ti+++ + H 2 = TiO++ + Fe++ + 2 H+ does not oxidize Fe* 4
"
'.
the basis of these observations, select (a) the strongest (b) the strongest reducing agent, oxidizing agent, If the data are insufficient to permit a decision, M " write in the word undetermined.
,
On
Questions 18,
19, 20,
necessarily equivalent but are always more the basis of the observations given, mark those known to be all substances known to be absent, mark and mark ? those whose presence is in doubt. 1 present,
made by selecting one The amounts are not

than mere traces.
and 21 represent hypothetical "unknowns" or more of the substances listed in each case.
On
18.
BaC0 3
Na 2 S0
4,
CaCL,
A1(NO 3 ) 3
(NH 4 ) 2S0 4
KOH
Treatment with toater gives a white residue, A, and a solution, B. The residue, A, filtered out and washed, is insoluble in dilute HC1. The solution, B, shows a violet flame test without
^See Appendix II for answers.

effervescence,
19.
431
using cobalt glass, and upon treatment with dilute HC1 it gives and a white ppt. soluble in excess of the acid.
ZnS,
PbCl 2
Fed,,
CrCl 3
KHSO
HgS
Treatment with
,
0.3 M-HC1 gives a black ppt., A, and a solution, B. The ppt., A, after filtration and washing, dissolves in hot 2 7kf-HNO 3 except for a small dirty yellow residue. The solution, B, treated with excess of 6 Jtf-NaOH, gives a green solution
and no ppt.
20. AlCla,
NH N0
4
,
3,
,
CuSO 4
SnCl 2
Na 2 CO Hg 2 Cl 2
3,
CaO,
Cr 2 O 7
Pb(NO 3 ) 2
Treatment with water gives an

a white ppt., which, after
affected
21. Zn,
odorless, yellow solution,
and
filtration
by
either
S or
NH
and washing,
Ag,
is
not visibly
3.
Sn,
Fe,
Hg,
PbO 2
When
treated with hot 2 Af-HCI, the
22.
on passing in H 2 S. has an atomic number of 10. Atom Y has 7 valence electrons, with 2 electrons in the group below the valence group. Atom Z has 11 more extra nuclear electrons than Y. Atom Q has 2 valence electrons, with 18 in the underlying level. On the
yields a black ppt.
gas, a yellow solution
and a white
residue.
unknown gives a pungent The yellow solution
Atom
basis of these figures, supply the following information. The .......... (b) of formula of: (a) the most stable ion of
.......... , (c) the moelcule of the free element .......... (e) the most (d) the molecule of the element basic hydroxide .......... (/) the most stable binary compound with hydrogen .......... (g) the most probable ammonia complex ion .......... (h) the hydroxide most likely to be amphoteric ........... 23. Which solvent in the following list:
,
Z ..........
Y
,
(a) 0.3
(6) 0.3
N-H SO 4
2
(c)
JV-HC1
(d)
6 M-NaOH 6 Jlf-NH 4
(e)
CC1 4
OH
(/)
NH
(g)
Br 2 (aq.)
SH(aq.)
would be most
(a)
(6)
(c)
effective (answer
a, b, c, etc.) for dissolving
CaC 2 4 ....... Ag C0 3 .......

2
(d)
24.
HgO .......... (/) How many valence electron? (d) CP ...... (a) Na .....
by writing only the letten each of the following PbCr0 4 ...... (g) C 24 H 50 ......... HgS ......... (*) Hg 2 Br 2 ........ SnS, ......... (f) Pb(OH) 2 .......
are there in each of the following? ..... 3 ..... (j) (g)
NH
SO"
(f)CaO
432
25. 112 cc. of C1 2 at 1 0.2
table.
APPENDIX
C. is passed into 100 cc. of atmosphere and Af-FeCU. Supply the numbers called for in the following
Before passing in
CU
Cone.
After passing in Cli
No. of moles
No. of moles
Cone.
Fe++ Fe+++
cr
Cl2
26.
in gas
electric cell consists of
An
an electrode of platinum in contact with gaseous hydrogen and another of PbC>2, both electrodes dipping into 0.1 M-H 2 SO4. Write equations for
(a)
The reaction at the hydrogen electrode The reaction at the PbO 2 electrode (6) (c) The total cell reaction The voltage of the cell would be increased, decreased, unaffected by (cross out two) 0.2 Jlf-H 2 S0 4 The oxidizing agent is the substituting
.
,
reducing agent
is
APPENDIX
II
ANSWERS TO EXERCISES
AT THE ENDS OF CHAPTERS
434
APPENDIX
II
Chapter VI
Exercises
4.
Answers
2
moles
5.
6.
7.
(a)
0.01
M;
(b)
0.02
N.
(a)
(a)
(6)
(c)
0.01 Af; (6) 0.02 tf. 0.02 equiv.
0.01
mole
(<0
8.
0.02 equiv. 0.73 g.

2 AT; (b)
1
(a)
IT;
to
9.
98g./l. 0.005 equiv., 0.20 g.; 0.185 g.

0.1
10.
N.
Chapter
2.
VH
Answers A/7 = -42.0
Exercises
kcal.
5.
Exercises
Answers
0.13*
1.1*
3. 4.
(a)
A//= -114 kcal. A// = -22.9 kcal.

Less
6.
7.
0.44*
ANSWERS TO EXERCISES
Chapter VIII
Exercises
12.
(a)
(b)
435
Answers
0.025 equiv./l. 0.425 g./l. 0.004 or 0.4% (b) 0.012 M.
1.988
15.
16.
(a)
(c)
M.
Chapter
6.
XH
Answers
10- 3
5.5
Exercises
Exercises
12.
(a)
8.
(a)
(b)
10~ 5 10~ 4 1.5 7 X 10- 5 4.5 X IO- 6 10- 3 25 cc.
X X
w
17.
18.
(0)
increase
effect
no
(d)
decrease io- 13 io- 5

4.7
19.
Chapter XIII
Exercises
28. 29.
Answers
Exercises
30.
Answers
0.027
5.6
(OH) =
3
10~ 3
31.
10
Chapter
9.
XXI
2.81.
10.
14.
15.
Increase, (d), (6), (a) 0.003
0.005
2.4
16.
17.
8
7
18. 19.
X X
IO- 4 IO- 8 IO- 7
0.1
436
APPENDIX
II
ANSWERS TO SAMPLE FINAL EXAMINATION QUESTIONS FOR THE SECOND SEMESTER

Question
1
Page 428
428 428 429
431 431
3 4
12
SnCl 2 +, Fe 2 (SO 4 )3-, KHSO 4 +, K 2 Cr 2O7 +, Hg2 Cl 2 -, FeSO 4 -, Ba(NO s ) +, ZnClj ? PbCU+, SnCl 2 +, ZnSO 4 ?, K 2 Cr 2O 7 +, Fe2(S0 4),+, Pb0 2 -. KHS0 4 +, Pb(NO 3 ) 2 -, NaNO 3 ? (NH 4) 2 CrO 4 +, BaCO 3 -, KC1 ?
Pb(NO 3 ) 2 +, CuSO 4 - HgCl 2 +, ZnCl 2 (NH 4 ) 2S0 4 +, K 2 CrO 4 -, NaNO s ? Zn?,Cu -,Ag+,Fe+,Al?
,
?,
13
AgNO 3 +, Hg 2 CU +, KN0 3 Na S0 4 ?, HgCU +

2
?,
NH
C1
+,
14 18 19
431
432
433 433
FeS +, Cr(OH) s +, BaCO 3 NaCl -, S +, NH 4 C1 ? BaCO 3 +, Na2S0 4 -, CaCl 2 -, Al(NO s)s +, (NH 4) 2S0 4 +, KOH + ZnS +, PbCl 2 +, Fed* -, CrCU +,
,
KNO
KHSO
20
4 ?,
21
433
NH 4 N0 3 -, Na2 CO 3 ?, CaO ? or -, K 2Cr 2 7 +, Pb(N0 3 ) 2 -, CuS0 4 -, SnCl 2 -, Hg 2 Cl 2 Zn ?, Sn ?, Fe +, Hg ?, Ag +, PbOg

A1CU +,
HgS -
INDEX
Acetates, zuj, zui Acetic acid, 101, 186, 204 Acetone, 142, 341
Ammonia
continued
synthesis, 240 system of acids
and
bases,
400
Acetylene, 337 Acids, 101 if.
Ammonium
hydroxide, 140 ionization, 186

ion
degree of ionization, 137 nomenclature, 156 organic, 203, 342 polybasic, 141 strength, 139, 312
systems, 103, titration, 107
Ammonium
hydrolysis, 206 solution of bases by, 210
Amphiprotics, 403 Amphoterics, 214, 219

Analysis, 11 gravimetric, 107
399
if.
weak, 139 Acid-base systems, 103, 399 Acid salts, 158 Acidimetry, 107 Actinide series, 323 Activation energy, 167
Adsorption, 357 Air, density, 69 Albumen, 212, 359, 369
Alcohol, 142,
groups
ff.
in,
216
volumetric, 107 Anhydrides, 102

Aniline, 346, 375, 382
Anions, 131, 272 Anode, 131, 272
Anthracene, 347, 378 Antimonic acid, 314
339
Antimony sulfides, Aqua regia, 264
214, 314
Aldehydes, 341
Aliphatic compounds, 344 Alkalimetry, 107
Alkalis, 102
Argon, 84 Aromatic compounds, 344

Arsenic
acids,
314
214
ff.
Alpha particles, 285
oxidation numbers, 149

sulfides,
Aluminum
chloride, 223
Arsine, 312
hydroxide, 211, 223 oxidation, 263 ft. oxide, 210

sulfate, 361 Americium, 293, 307, 319 Amines, 344 Amino acids, 212, 344
Atomic numbers, 85, 306 Atomic radii, 81, 309 Atomic weights
calculation of, 32 choice of, 24
scales,
ff.
282
table, 13
Ammonia
complexes, 202, 318
liquid, 142,
Atoms, 14
structure, 80
ff.,
279
ff.
400
Avogadro number, 26 437
438
Avogadro's
rule,
INDEX
53
Baking soda, 207
Calomel electrode, 258 Calorie, 119

Calorimeter, 119 Calx, 12 Carbohydrates, 124
Barium peroxide, 147 Barium salts, 187, 317

Bases, 102, 139, 399 Basic salts, 158, 217
Batteries, 254, 270
Carbon, 416 compounds, 328

disulfide,
ff.
Benzaldehyde, 346 Benzene, 345, 380 Benzoic acid, 346 Benzyl alcohol, 346 Beryllium, 318 Beta rays, 298 Bicarbonate ion, 186, 389 Bichromates, 159, 267
dioxide, 49, 73, 386
ff.,
421
376
tetrachloride, 93, 329,
376
Binary compounds, 155 Bismuth compounds, 158 Bismuth sulfide, 214

Bisulfate ion, 140, 186
Bisulfates, 159
Carbonates, 198, 386 Carboxyl, 342 Catalysis, 169, 189 Cathode, 131, 272 rays, 280 Cations, 131, 272 Cellulose, 348 Chemical affinity, 260
Boiling point, 10, 381 Boltzmann constant, 48
Bonds,
89,
290
ff.,
329
Bond
angles, 421
Borax, 207 Boric acid, 101, 207 Boyle's law, 41 British thermal unit, 119
Chemical equations, 30, 71, 246 Chemical equilibrium, 193 ff. Chemical reactions, 4 control, 171, 193, 232 volume changes in, 71 weight relations in, 19, 28 Chemistry, 1 Chlorate ion, 157, 269 Chlorides, heat of formation, 99
Chlorine
Bromine, 90, 266, 376
atom, 85
molecule, 90 reduction, 266
solubility, 376 Chloroform, 329
Brownian movement, 355 Buffers, 325, 394

Buret, 108
Butadiene, 350 Butane, 332 Butyric acid, 342
Chromate ion, 248, 252, 269, 316 Chromic ion, 246, 268, 316 Chromic oxide, 211
Chromite
ion, 248, 252,
Cadmium
202 halides, 141, 218 sulfide, 187, 218 Calcium, 262
269
complex
ions,
Chromium, 316
compounds, 316
hydroxide, 211, Citric acid, 242
248
carbonate, 187, 216, 222, 417

chloride, 317
fluoride,
Cloud chamber, 287

Coagulation, 359 Cobalt, 316
187
hydroxide, 187, 317 oxalate, 187
phosphates, 201
sulfate, 187, 222,
compounds, 316 complex ions, 202 sulfide, 213, 316

Colloids, 353
384
INDEX
Combining proportions, 19
133
ff.,
439
continued
ff.
87,
Dissociation
heat, 90
electrolytic, 127
Combustion, 165
Complex ions, 202 Compounds, 11

Concentration, 107
effect effect
ff.,
318
Dyes, 347, 361

Electric batteries, 254, 270
ff.
stability of, 95, 311
Electric dipoles, 91, 379

ff.
on equilibrium, 172 on velocity, 165 ff.
Electricity per gram-ion, 132
molal, molar, 110
Electrochemical series, 98 Electrolysis, 130 ff.

Electrolytes, 130 Electrolytic dissociation, 127
ff.
normal, 110
of gases, 41
Contact process, 238 Coordination number, 150 Copper, 253, 316 complex ions, 202, 318
oxidation, 253
refining, 261
sulfide, 187, 213, 316,
ff.
Electrolytic refining, 261 Electrolytic separations, 261
Electromotive force, 254 Electron, 81, 254, 280

clouds, 82
ff.
donor system, 389

385
formulas, 88, 104, 149, 330
pair bonds, 89, 150, 290, 329 Electronegativity, 92, 420
Cotton, 348
Coulomb,
Crystal
lattices,
27, 132
Covalence, 89, 150, 290, 329
93
ff.
Elements, 11 ff. atomic weights, 13 nomenclature, 154

Emulsions,
6, 354, 364 Endothermic reactions, 121 Energy levels, 286
structure, 413
Curium, 293, 307, 319 Cyanides, 203, 206
Cyanide process, 265 Cyclic compounds, 344

Cyclotron, 301
Enzymes, 171
Equations
interpretation, 30, 71 oxidation-reduction, 246
writing, 151, 246
Dalton's law, 50
Deduction, 19
Definite proportions, 21 Democritus, 19
Equilibrium
concentration, 172
pressure, 232
ff.
ff.
Density, 317
Deuterium, 282, 284 Deuteron, 297 Diamond, 94, 416
temperature, 232 types, 193 ff.

Equivalent,
acid-base, 110
ff.
Dichromate
ion, 159, 248,
267
electrochemical, 132
Esters, 343
Dielectric constant, 91, 142 Diffusion, 55, 356
Ethane, 332
Ethers, 341, 376
Dioxane, 408 Diphenyl, 346

Dipole moment, 91, 379 Dispersed systems, 353
Dissociation
constants, 185
ff.
Ethyl
acetate, 346
alcohol, 142,
339
Ethylene, 337, 348
Examinations, 423
INDEX
Exothermic reactions, 121
Explosions, 166
Fahrenheit
scale,
45
132
Gram-atoms, 25 Gram-molecules, 12 Graphite, 416
Faraday of
Gypsum, 173
Haber
process, 240 Halides, 203
electricity,
Fats, 124, 343 Ferric
hydroxide, 359
ion, reduction,
267
complex ions, 203, 225 oxide, 210

Ferricyanide ion, 203 Ferrocyanide ion, 203 Ferrous
hydroxide, 187, 271, 359 ion, oxidation, 267
Hard water, 207, 391 Heat capacity, 55 Heat of

activation, 167
dissociation,
90
formation, 120
neutralization, 136
reaction, 4, 118, 136
214 Films, liquid, 363 Fission, nuclear, 303 Fluorine, 90, 266 Foams, 354 Fog, 6, 354 Foods, fuel value, 124 Formaldehyde, 330 Formic acid, 342
sulfide, 187,
Helium, 84 Hemoglobin, 212 Henry's law, 53, 387 Heptane, 334, 376 Heterogeneous systems,
6,
353
ff.
Homogeneous systems, 6
Hydrocarbons, 328 ff. Hydrochloric acid, 140, 193 Hydrocyanic acid, 186, 227 Hydrofluoric acid, 194, 381 Hydrogen atom, 83, 287
Formulas, 14
calculation, 33
electronic, 88, 104, 149,
330
empirical, 33
ionic, 133 meaning, 26 Free energy, 260
Hydrogen bond, 380, 400 Hydrogen electrode, 257 Hydrogen gas, 13, 90
solubility,
376
Freezing point lowering, 76, 128 Fused salts, 142

Gallium, 373 Galvanized iron, 254
deposition, 262 Hydrogen ion concentration, 140, 18 1

225, 258
Hydrogen Hydrogen bond
peroxide, 251, 268

sulfide
boiling point, 381

angle, 421 ionization, 186
Gamma
rays, 297
ff.
Gases, 36
Gas constant, 47
Gelatin, 357, 368
oxidation, 270
stability,
312
ff.,
Germanium, 319
Glue, 357
Glycerol, 340 Glycol, 340
Hydrolysis, 204
226, 389
ff.
Hydrophilic colloids, 366 Hydrophobic colloids, 366

Hydrosulfide ion, 186
Gold
colloidal,
369
Hydroxides, solubilities, 187, 198, 203 219, 319
complex ions, 203, 265 solution of, 265
Hypochlorous
Hypochlorite ion, 100, 157, 269 acid, 157
INDEX
Hypophosphorous
Ice,
441
of conservation of mass, of mass action, 178 ff.
acid,
314
382
Law Law Law
20
Indicators, 108, 200, 209
of simple multiple proportions, 22 Lead, 99, 253, 270, 414 acetate, 141
Indigo, 347
Induction, 19
Ink, 224
Insulin, 212
bromide, 187
chloride, 141, 188, 198
Intermolecular forces, 372 Iodide ion, 266, 268

Iodine
chloride, 91, 94
chromate, 187, 195 dioxide, 270 hydroxide, 187, 211

sulfate, 173, 187, 198,
sulfide, 187,
201
213
molecule, 90 oxidation, 269

solubility,
Le
Chatelier's theorem, 178
Leucite, 313
376
Limestone, 216
Lyophilic colloids, 367
reduction, 266 Ionic bonds, 85 ff.
Lyophobic
ff.
colloids,
367
Ionic charges, 146 Ionic compounds, 90

Ionic radii, 81, 309 lonization, 127 ff.
constants, 186 degree of, 137
MacLeod
gage, 62
Magnesium, 270
chloride, 317
hydroxide, 187, 190, 209, 317

sulfate,
317
potentials, of atoms,
310
Malonic
acid,
342
of,
Ions, 85
Manganese compounds, 316

Mass, conservation
20
migration, 130 Iron

crystal structure, 414
Mass
ff.,
law, 178
ff.
316 Isoelectric point, 212 Isomers molecular, 328 nuclear, 300 optical, 331 Isotopes, 281
oxidation, 253
Jellies,
Mayonnaise, 363 McMillan, 320

Melting points,
Mendeteeff, 306
9,
198
Mercuric
chloride, 141
cyanide, 141
sulfide, 187,
214
367
Mercury, 252 Metabolic oxidation, 124

Metals, 90
densities,
Joule, 118
317
of,
Kelvin
scale,
44
oxidation
262
142, 335
Kernel, atomic, 87 Ketones, 341

Koroseal, 348 Kinetic theory, 36
Methane, 329 Methyl alcohol,

Migration
ff.,
162
ff.
colloidal particles,
ions,
358
Krypton, 84, 281

Lakes, 361
Lattices, crystal, 93, 413
130
Millikan, 26
Mole, 12 Molecular weights,
15,
63
ft.
442
Molecules, 15, 23, 55, 63, 66
INDEX
Partial pressures, 50 Pepsin, 212, 368
Molybdenum, 312
Mordants, 361 Mustard gas, 352
Naphthalene, 378 Neutralization, 199 Neon, 84 Neptunium, 306, 322
Neutron, 81 Nickel compounds, 216, 271, 316
Nitrates, solubility, 198 Nitric acid
Peptization, 368 Perchlorate ion, 157
Periodic System, 306
ff.
Permanganate
Peroxides, 147
ion, 249, 267,
316
Petroleum, 244, 333 Phase, 6
Phenanthrene, 378 Phenol, 205, 346, 380 Phenyl radical, 346

Phosphates, 194, 217, 225 Phosphine, 312
oxidizing agent, 267
preparation, 194 Nitric oxide, 120, 169, 183, 237, 241
Phosphoric acid, 141, 160, 314 Phosphorus acid, 160, 314
Nitrobenzene, 346, 380 Nitrogen, 10

solubility,
Phosphorus
molecule, 15 oxidation numbers, 315
solubility,
376
Nitrous acid, 183, 267, 314 Noble gases, 84 Noble metals, 264 Normal concentration, 110 Nucleus of the atom, 82, 288 Nylon, 349
Octet, 84, 295 Oleic acid, 342
Olein, 343, 345 Organic chemistry, 328
376
trichloride, 208 Plaster of Paris, 173
Platinum, 264
complex
Plexiglass,
ions,
202
349
Oxalates, 203 Oxalic acid, 101, 342
Oxidation, 147, 246
ff .
ff.,
Oxidation number, 146, 246 Oxides, 102, 407 solution by acids, 210 Oxy-acids, 157 Oxygen, 10, 24 atom, 81 ff., 282 gas, 49 molecule, 65 reduction, 265 Ozone, 66, 166, 421
Palladium, 319 Palmitic acid, 342 Palmitin, 343
Paraffins,
314
ion, 220 Plutonium, 304, 322 Polarity, 90 ff., 379 Polymers, 347 Polysulfide ions, 215 Positive rays, 281 Positron, 298 Potassium chlorate, 157 chloride, 157 hydroxide, 102 Precipitation, 198
Plumbite
Pressure, 36
effect
ff.
on equilibrium, 232 partial, 50
Propane, 332^
Properties, 2 Propionic acid, 342
Protective colloids, 367

Proteins, 124, 345
332
Protons, 81, 296 Proton donors, 402 Ptyalin, 171
INDEX
Pure substances, 8 Pyridine, 407
Pyro-acids, 160
443
Soap, 363 Sodium, 253 atom, 85

bicarbonate, 207, 381
borate, 207 carbonate, 207, 381
chloride, 415
Qualitative analysis, 107 Quantitative analysis, 107
Quantum Theory,
Radicals, 335
83,
286
hydroxide, 102, 224 phenolate, 205

silicate,
Radioactivity, 297, 320 Radii, ionic, 309
207
3*72
Solid solutions, 9
Solubility, 195
electrolytes,
ff.,
Radium, 301 Radon, 84 Rankine scale, 45

Raoult's law, 75, 375 Reactions, 175 ff.
velocity, 162
ff.
ff.
383
gases, 52, 375
product, 186, 316

soiids,
377 355
Solutions, 8
colloidal,
ff.
Reagent, 107 Reduction, 147, 246
fraction at ion, 11 process, 128

solid,
Refining, electrolytic, 261
Resonance, 345 Rubber, 349

Salicylic acid,
Salts,
standardizing, 115
347
158
ff.
100
acid
and
basic,
fused, 142
nomenclature, 154
Solvay process, 218, 395 Speed of reactions, 162 ff. Spontaneous combustion, 166 Stability of compounds, 95 ff. Standard conditions, gases, 46 Standard solutions, 115
383
Stannic
acid, 211
sulfide,
solubilities, 198, 317,
weak, 140 Scientific method, 5 Seaborg, 320 Silicic acids, 160, 359
Silicon chloride, 350,
Silicones,
213
Stannous
376
hydroxide, 187, 211 ion, 267
sulfide, 187,
350
213
Silver
Stearic acid, 342
cleaning, 261
colloidal,
369
ions, 202,
Stearin, 343 Steel, 7
complex
220
ff.
Stibine, 312
ion, reduction,
266
oxalate, 187
Storage batteries, 270 Strontium compounds, 317, 384

Substances, definition, 2 Succinic acid, 342
Sugar, 129, 170
Sulfates, 198, 384
oxidation, 253, 261

oxide, 213
salts, 187, 196,
ff.
220
sulfate, 187
sulfide, 187, 213, 261 Simple multiple proportions! 22 Smoke, 6, 354
Sulfide ion
concentration, 187
Sulfides, 187, 212
ff.
INDEX
Sulfides
continued
solubility in acids, 212, 270 solubility in sulfide ion, 214
Transformations, 222 Transition elements, 316
solubility in water, 190, 214 Sulfo-acids, 157
Vanadium compounds, 316 Van der Waals' equation, 49

Valence, 146
ff.
Sulfur
dioxide, 169, 182, 235, 268, 421
Valence electrons, 88, 290
molecule, 381 oxidation numbers, 148

trioxide, 182, 235
Vapor pressure
pure liquids, 52 solutions, 74, 375
Velocity molecules, 55, 168 reactions, 162 ff.
Volatility, 193
Sulf uric acid
manufacture, 169, 235 reduction, 267 strength, 313 structure, 149

volatility, 193
Volume changes
in reactions,
65
Volumetric analysis, 107
Sulfurous acid, 157 oxidation, 267

strength, 313
Surface
effects, 164,
353
Washing soda, 207 Water bond angle, 421

hydrogen bonds
softening, 392
in,
Suspensions, 355 Symbols, 25

Synthesis, 11
380, 400
ionization, 142, 199,
260
solvent power, 127, 380
Tartaric acid, 343
Temperature
absolute, 42
effect
ff.
Weak acids and bases, 139, Weak salts, 140, 201, 218
Weight
relations, 19,
185, 201
28
effect
effect
on equilibrium, 235 ff. on gases, 36 on reaction velocity, 163
Wetting, 364
Wool, 212, 348

ff.
Tensile strength, 318 Thermochemistry, 118

Thiosulfates, 149
Xenon, 84
X-rays, 27, 297
Zero, absolute, 42
Zinc, 253
ff.
Thomson, J. J., 280 Thorium, 300 Tin (see stannic, stannous) Titanium compounds, 316
Titration, 107 Toluene, 346
complex
ions, 202, 219,
318
hydroxide, 187, 211, 219 oxidation, 253 ff.

sulfide, 187,
214
Reference Book of
Inorganic Chemistry

NEW YORK
DALLAS
ATLANTA
CHICAGO SAN FRANCISCO
LONDON
MANILA

OF CANADA, LIMITED
TORONTO
REFERENCE BOOK
of Inorganic Chemistry
BY WENDELL
M.
LATIMER
Professor of Chemistry in the University of California
AND JOEL
H.
HILDEBRAND
Professor of Chemistry in the University of California
THIRD EDITION
The
Macmillan
NEW YORK
Company
THIRD EDITION COPYRIGHT, 1951
By
AIL RIGHTS RESERVED NO PART OF THIS BOOK MAY 3 REPRODUCED IN ANY FORM WITHOUT PERMISSION IN WRITING FROM THE PUBLISHER, EXCEPT BY A REVIEWER WHO WISHES QUOTE BRIEF PASSAGES IN CONNECTION WITH A REVIEW WRITTEN FOR INCLUSION IN M VGAZINE OR NEWSPAPEK
Printed in the United States of America

Fifth Printing,
1956
Ffrst
and second
editions copyrighted
and published, 1929 and 194O
Bv The Macmillan Company
PREFACE TO THE THIRD EDITION

In preparing this third edition, we have kept constantly mind our original objective, a single convenient volume to which the chemist may turn to find the facts or data
in
relevant to the majority of problems which he may enIncreased emphasis has been placed upon thermodynamical data, such as oxidation potentials, equilibrium
counter.
constants and free energies, since they may be used to express so concisely the tendency of a reaction to go, and
the nature of the equilibrium state. Oxidation-reduction potential diagrams have now been given for almost every element.
'
Actinium and the heavier elements have been treated in " and title, "The Actinide Elements, considerable attention has been given to the chemistry of plutonium and the other new transuranium elements. The chapter on the atomic nucleus has been completely rea
new chapter with the
written to include
the general types of nuclear reactions. discussion of nuclear fission and various pile reactors has
all
At the end of this chapter, the table of nuclear properties has been extended to include all known
been added.
isotopes.
New investigations have been noted in the general field of inorganic chemistry and additions have been made to
most chapters, especially those dealing with boron, phosphorus, and silicon. Sections on the chemical industries have been brought up to date, and in many cases, greatly
expanded.
The
text has not been
"
written
down"
to the level of
elementary students. A foreign language may be mastered either by starting with a primer or by hearing the language spoken and used in every day life. In the first year chemis-
PREFACE TO THE THIRD EDITION

try course at the University of California, both methods o W< teaching the language of chemistry are employed.
believe that,
by the end
of the year, the students cat
acquire the facility to read and understand the literature o inorganic chemistry, and that the ability to use the Refer
be of great value to them in their subsequen professional work.

ence
Book
will
W. M.
BERKELEY, CALIFORNIA March, 1951
L.
PREFACE TO THE
FIRST EDITION
This book represents the fulfillment of a plan, long cherished, of providing a volume of descriptive chemistry " to complete the series begun with Principles of Chem" which adheres strictly to its title, by Hildebrand, istry and continued with the " Course in General Chemistry" by Bray and Latimer, which presents a laboratory course.
The
rather radical experiment in teaching general chembegun in the University of California in 1912, has been somewhat hampered by the lack of a reference book on descriptive chemistry employing the language and the
istry,
point of view adopted for our instructional scheme. " This Reference Book of Inorganic Chemistry" has been written as a reference book rather than a text. The authors have sought to present essential chemical facts briefly, clearly, and in due relation to other facts and principles. The instructor using it will have to map out his own course, following whatever order of arrangement appeals to him.
,The numbering of paragraphs will make it possible for him to assign for study material selected from any desired We feel that many teachers will portion of the book. welcome the greater freedom thus afforded of developing their own pedagogical methods. Chemical properties have been widely related to atomic
structures and sizes. These ideas, although new, and subject to revision, are so illuminating that they appeal strongly to the imagination. Moreover, they are not difficult to grasp;
many
concepts traditionally courses are far more elusive.
introduced into freshman
The formulas of many compounds have been given in terms of the Lewis theory of valence, not with the idea that these formulas represent the definite locations of the
vii
vfii
PREFACE TO THE
FIRST
EDITION
electrons, but rather to call attention to the importance of considering the total number of electrons or electron pairs in a molecule. The extensive tabulation of "half reaction*' potentials, equivalent to free energy values, will enable one to predict the direction and driving force of an immense number of reactions. Many of these potentials have been calculated
for this
book from reaction heats and entropy values, and
have not heretofore been published. We have treated industrial processes with emphasis upon their chemistry, relation to other industries, and economic magnitude, rather than upon their mechanical features.
used in some texts, have been
Illustrations of industrial processes, of the sort extensively left to the instructor to pro-
vide, as he can do so far more adequately, by the use of lantern slides and motion pictures. Many excellent films
are
now available at a nominal expense. The book contains much more material than
the average
student, or even the average chemist, can assimilate. " " believe, however, that students should be exposed to a
far greater range of subject matter than is usually prehave found the appetite and assimilative capacsented. of the superior students to be almost unlimited, and ity
We
We
For the average student, the presence of this extra material in the book does no more damage than the unordered articles listed on a restaurant menu. We anticipate that this kind of a book will prove useful, not only to the freshman student, but also to the student who desires a reference book in advanced courses in chemistry and allied subjects; and further that teachers and
see
we
no value
in
an
intellectual diet
list.
industrial chemists will also find in

their questions.
it
answers to
tables,
many
mass
of of
To
increase its usefulness, a large
data has been included in the form of

text
both in the
and
in the various appendices.
In the endeavor to keeo the size and cost of the book at
PREFACE TO THE
FIRST
EDITION
ix
a low
figure, it was decided to omit references to the original sources of material, although in many instances such
scientific value. Frethe more comprehensive treatises, especially: Gmelin-Kraut's Handbuch der anorganischen Chemie Abegg and Auerbach Handbuch der an-
references
would be of
historical
and
quent use has been

;
made
of
organischen Chemie A Text-Book of Inorganic Chemistry, Edited by Friend A Comprehensive Treatise on Inorganic and Theoretical Chemistry by Mellor Lexikon der anorganischen Verbindungen by Hoffman; Landolt-Bornstein Tabellen; and The International Critical Tables.
;
;
indebted to their colleagues in the Department of Chemistry of the University of California, especially to Professors G. N. Lewis and W. C. Bray, not only for specific criticisms and suggestions, but for many of the general ideas upon which our interpretation of the facts of inorganic chemistry has been constructed.
are
The authors
much
WENDELL M. LATIMER
JOEL H. HILDEBRAND
BERKELEY, CALIFORNIA
December, 1923.
CONTENTS
PTER
I.
PAGE
HYDROGEN
II.
INERT GASES: HELIUM, NEON, ARGON, KRYP13 19
TON, XENON, RADON OXYGEN ivait^JA-' IV. GROUP I. ALKALI METALS. V^_vrTV. ... V. GROUP II. ALKALINE EARTH METALS VI. GROUP III. gQgQN, AjbUMINJtM VII. SUBGROUP I. COPPED S W; SILVER, AND GOLD. VIII. SUBGROUP II. ZINC, CADMIUM, AND MERCURY IX. SUBGROUP III. THALLIUM, INDIUM, AND THALIII.
.'.
.
.
36 57 80 100
129
LIUM 148 i X. GROUP VII/^ THE HALOGENS: FLOURINE, CpLORiim BROMINE, IODINE, ASTATINE.. 156 XI. GROTJP V. NITROGEN, PHOSPHORUS, ARSE186 NIC, ANTIMONY, AND BISMUTH XII. GROUP VI. SULFUR, SELENIUM, TELLURIUM,
XIII.
AND POLONIUM CARBON
XIV. SILICON
243 270 309
XV. THE METALS OF GROUP IV. TITANIUM, ZIRCONIUJM, HAFNIUM, AND GERMANIUM, TIN* f. LEAD XVI. SUBGROUP V. VANADIUM, NIOBIUM, TANTALUM XVII. SUBGROUP VI. CHROMIUM, MOLYBDENUM,
.
.
331
357
369 TUNGSTEN, (WOLFRAM) XVIII. SUBGROUP VII. MANGANESE, TECHNETIUM, 386 7 RHB&IUM 399 XIX. IRO^VCOBALT AND NICKEL 433 XX. TPLATINUM AND PALLADIUM METALS XXI. SCANDIUM^ YTTRIUM, AND THE RARE EARTH 451 ELEMENTS 462 XXII. THE ACTINIDE ELEMENTS 484 XXIII. NUCLEAR REACTIONS
GLOSSARY
513
xii
CONTENTS
Appendices
PAGE
I.
SUMMARY OF FUNDAMENTAL CONCEPTS RELATING TO ELECTROLYTIC OXIDATION AND

REDUCTION STANDARD OXIDATION-REDUCTION
TIALS
525
II.
POTEN528
III.
IV.
V.
536 FREE ENERGY VALUES AND THEIR USE 541 lONIZATION OF STRONG ELECTROLYTES CRYSTAL FORMS AND TYPES OF CRYSTAL LATTICE
VI. QUALITATIVE ANALYSIS

VII. VIII.
IX.
X.
XI.
XII. XIII. INDICATORS
SCHEME STRUCTURE OF MOLECULES AND IONS DENSITY OF WATER DENSITY OF MERCURY EQUILIBRIUM PRESSURE OF WATER WATER VAPOR 560 SOLUBILITY PRODUCTS AND ACID IONIZATION 561 CONSTANTS 564 BUFFER SOLUTIONS
565
544 548 556 558 559
XIV. CHANGE OF RESISTANCE OF METALS WITH TEMPERATURE XV. SPECIFIC HEAT OF METALS AND COMPOUNDS AT Low TEMPERATURES XVI. COVALENT BOND ENERGIES AND ATOMIC RADII XVII. TABLE OF CONVERSION FACTORS XVIII. THE ELECTRON STRUCTURE OF THE ELEMENTS XIX. ABUNDANCES OF THE ELEMENTS XX. TABLE OF DENSITIES, MELTING POINTS, BOILING POINTS, COLORS, AND SOLUBILITIES OF INORGANIC COMPOUNDS
INDEX
PERIODIC TABLE
566
567 568 570 572 575
577
601
Facing inside back cover

Inside back cover
ATOMIC WEIGHTS
Reference Book of
Inorganic Chemistry
Chapter
HYDROGEN
Structure of Hydrogen Atom. The element, hydrohas three isotopes, their mass numbers being one, two, gen, and three. The isotope of mass one is by far the most abundant; the hydrogen of ordinary water contains 0.0156 per cent of the isotope with mass two, and practically none The latter is formed in of the isotope with mass three. certain nuclear reactions but undergoes radioactive decom1.
position.
The mass two

is
mass three isotope designate isotopes
isotope is called deuterium and the called tritium. It is not customary to
by special names, but in this case the difference in the masses greatly exceeds that of percentage any two isotopes of the other elements and there is a
correspondingly greater divergence in their physical and chemical properties.
The hydrogen atom (mass one isotope) is composed of two corpuscles; one, the proton, is positively charged and the other, the electron, is negatively charged. The mass of
the proton
about 1,850 times that of the electron but the electrical charges, though opposite in sign, are equal in magnitude. The atom has a large number of energy states representing different configurations of the electron and proton. The
is
values for the energy of the atom in these different states may be expressed as a close approximation by the very
simple relation
E =
13
54Z ~
volts per unit charge,
where
REFERENCE
BOOK OF INORGANIC CHEMISTRY
[Ch.
is
the
the charge on the proton (equal to unity) and N, called quantum number, is any integer from 1 to oo The nor,
mal atom
energy
5,
is
in the first
quantum
state
(N =
1)
and the
in volts required to move the electron to the 2, 3, 4, oo When quantum states is shown in Fig. 1.
JV
a=
oo
the energy
is
zero.
This corresponds to the com-
plete separation of the electron

N
and proton, and the

is
total
energy required per unit charge as 13.54 volts.
given
When
the electron
moves from a
higher quantum level to a lower, the energy difference is emitted in the form
of light, whose frequency, v, is related to the energy difference, AJE, by the
equation, AE = hv, where h is a conLikewise stant ("Planck constant"). the atom in a lower quantum state may
absorb energy in the form of light of a given frequency and the electron thereby move to a quantum level of correspondFIG. 1. Energy levels in the hydrogen atom.
ingly higher energy. The spectral lines arising from electrons falling from outer
levels to the first
quantum
level are lar
out in the ultraviolet, but transitions from outer levels to the second quantum state give rise to the Balmer series which is in the visible spectrum. The highest frequency
in the hydrogen spectrum is, of course, that corresponding to the electron falling from the infinite quantum state.
to account for these quantum states by the electron as revolving about the proton in some picturing one of a number of possible orbits, which are circles or
Bohr has sought
These orbits are defined by the restriction that the of the system must always be some multiple, i.e. the quantum number, of a single fundamental quantity. The total quantum number was considered to be the sum of two other numbers, one giving the units of angular moellipses.
momentum
2]
HYDROGEN
is,
mentum and the other the units of radial momentum, that momentum in the direction of the radius. These numbers
the size and shape of the orbits. Figure 2 represents these
fix
orbits for the cotal
quantum number,
as
I, 2,
and
3,
and
angular given by the subscripts. The radius of the li orbit^ iaT

<!B2 9
the
momentum
x lofon;
While the existence of discrete energy states rests upon

experimental facts, the Bohr theory has had to be modified so that the orbits no longer have theh' former clear-cut
meaning. The changes are due to the discovery that some sort of wave motion is associated with a moving particle. This has led to modifications in the equations of motion The to give probabilities rather than precise answers.
orbits jire
generally referred to as eigen functionsTor orbitals, from which the probability of finding the electron in a given region mayJ}etleterminecL_ Figure 3 is a schematic
now
representation of the wave mechanic picture and may be considered as a composite of the electron in many positions
The electrons are to give an average electron den.sity. designated as s,p,d f,g'*- corresponding to 0, 1, 2, 3, 4
9
units of angular
2.
momentum. The same general quantum
relations as outlined
above
hold for the other elements, complicated, however, by the facts: (1) that the positive center is no longer a simple unit charge but a complex structure with a net positive charge equal to the atomic number, arid (2) that the number of electrons is not one, but a number equal to the atomic number. It is the distribution of these electrons among the various quantum states that determines the grouping of the elements into the so-called "chemical families/' The maximum number of electrons in any atom that can have the 2 = 1, the same total quantum number is 2JV e.g. for
REFERENCE

;
[Ch.
maximum number of electrons is 2

when
the
first
for
N=
2, it is 8.
Hence
complete with the second quantum the three electrons of the third element, element, helium, lithium, cannot all remain in the first level, but one of them With each succeeding element is forced into the second. of higher atomic number, the number of electrons in the second level increases until it is filled with eight electrons,
level is
i.e.
in neon.
Each
alkali
metal marks the beginning of a
FIG. 3. Different states of the hydrogen atom (after H. E. White): a, the atom with a 1 .s electron; b,2s electron; c, one of the states with a 2 p electron
in a magnetic field.
new quantum group and each

a group.
noble gas the completion of
Each orbital (Par. 1) contains a maximum of two electrons and the total number of electrons for any one value of the total quantum number, N, and radial quantum
number
two
s,
I is
2 (21
s electrons, for
+ 1). Thus for the first shell there are two the second two s and six p, for the third,
d,
six pj
and ten
and so on.
distribution of the electrons in the various

indicate that
it
complete table of the atoms is given in
of the electron has a quantized spin motion. However when an orbital contains two electrons, the resultant magnetic spin moment is zero, that is, the two spins are in opposite
Appendix XVIII. The magnetic properties
directions.
Occurrence of Hydrogen. Only about one per cent by weight of the earth's crust (outer 10 miles) is hydrogen.
3.
4]
HYDROGEN
if
is expressed in terms of the be stated that about sixteen per cent of all the atoms on the earth's surface are hydrogen, being second in abundance to oxygen. The major portion of the earth's hydrogen is combined with oxygen in water. It also frequently occurs combined with sulfur, carbon, nitrogen, and chlorine, and less frequently with the other halogens and phosphorus. Hydrogen is a constituent of all acids, and of all animal and vegetable tissue. Only a trace of free hydrogen is found in the atmosphere, but larger quantities are sometimes found in volcanic and other natural gases. Hydrogen appears to constitute 30 per cent of the mass of the sun and spectral analysis of light from the
However,
the composition
number
of atoms, it
may
hydrogen is by far the most abundant element in the universe (cf. Append. XIX). Atomic hydrogen combines to 4. Molecular Hydrogen. form the molecule H 2 Representing the proton by H, and as the electronic the electron by a dot, we may write formula of the molecule, indicating that the two electrons constitute a bond holding the protons together. Due to the spin of the protons, two forms of the molecule exist: para- with spin directions opposed and ortho- with the
stars indicates that
.
H H
:
room temperature sjj^sjhe^sanê. f ortho- Jin jin equilibrium mixture
At
the gas
para- and Equilibrium at the

is
boiling point gives almost pure para- but the change from the high temperature mixture is slow. It is however cata-
lyzed
by charcoal and other
surfaces.
The
boiling point of
Hydrogen has the lowest molecular weight and hence the smaHestTclensity of any substance, and, with the exception oTHefiun^rthe lowest mel,(mg point and the lowest ^boiling point. The gas is odorless, tastefess, and colorfess. The most important physical constants are collected in Table I. Hydrogen was JftrstJKquefied by Dewar (1898^. The gaTlrTexpanding from^KIgfi pressure to low pressure is
REFERENCE

TABLE
[Ch.
PHYSICAL CONSTANTS OF HYDROGEN

Melting point,
C A
cals.
259.2 13.9
Density 760
mm
g. /liter
at
and
0.08985
0,071
Heat of
mole
fusion,
per
Density of liquid g./cc
28
Boiling point,
Solubility
in
water at 25
252.7 20.4
vol. per 100 vol. of
0.
1.8
Heat
Heat
of vaporization, cals.
of dissociation,
cal.
Hz =
103,730
2H
218
241 32
per mole
per mole
Critical temperature,
C. A..
.
Per cent H 2 dissociated at 1 atm. total pressure
At 2,500
3,500
A A
1.3
29.7
Critical pressure, atmos.
20
heated at ordinary temperatures, but if cooled in liquid 185 C.), the sign of this heat is reversed. air ( Adis taken of this fact in the liquefaction process. Vantage
(For further discussion of liquefaction process cf. Ill 6.) of the nickel, palladium, platinum groups occlude or dissolve hydrogen to a remarkable degree. Under certain conditions one volume of palladium will take up almost 900 volumes of hydrogen at 20 and 1 atmosphere. (Cf. Palladium, XX 27.) Molecular hydrogen has a very
The metals
high relative rate of diffusion since this property is inversely proportional to the square root of the density. Thus the
densities of hydrogen and oxygen are in the ratio of 1/16 and hydrogen diffuses four times as fast as oxygen.
5.
Reactions of Hydrogen.
Hydrogen combines
directly
with most of the lighter elements, accompanied in the case of the more electronegative elements with the evolution of large amounts of energy e.g. a jet of hydrogen burns readily in an atmosphere of oxygen or chlorine, and its mixtures with these gases are highly explosive. The electron formulas of the compounds with the elements from lithium to fluorine are as follows:
;
6]
HYDROGEN
Be:
-B:
:C:
Element
Li-
:N:
:O:
:F:
Compound
Li:H
H HO
2
H H
H
H:O:H H:F:
H:Be:H H:B:H H>C:H H:N:H
From
CH
to
hedral symmetry. as indicated in the electron formula given above, but the hydrogens are located approximately at corners of a tetra-
the four pairs of electrons have tetraThus in 2 O the molecule is not linear
hedron.
BH
exists only as the dimer,
B 2H6
(cf.
VI
11).
The more
does
it
negative the element, the more completely tend to acquire the electrons of hydrogen, thus
leaving the hydrogen with a charge of + 1. The more positive elements, on the other hand, tend to lose their electrons to hydrogen, giving it a charge of 1, since, as mentioned
in
Paragraph
first
2,
there
is
room
for
two
electrons
in
hydrogen atom. In this quantum respect hydrogen resembles the halogen family, all members of which lack one electron of completing the noble gas
the
state of the
structure.
Hydrogen
in the
is
in water solutions
as hydride. The ion unstable with respect to the reaction

1
state
is
known
H- + H
= H + OH2
For the hydride potential see Appendix II. The details of the reactions of hydrogen will be discussed under the various elements, although the general reaction of hydrogen to hydrogen ion is to be considered under the following
topic.
6. Properties of the Hydrogen Ion, Hydrogen ion is the substance present in all solutions of strong acids and its properties are the familiar properties common to all acids, such as sour taste, characteristic color changes with organic indicators, e.g. the change of blue litmus to red, the neutralization of bases, and the solution of base metals.
REFERENCE
[Ch.
complete statement of the properties of hydrogen ion would include values for the degree of dissociation, volatility, and solubility of all of its compounds, since these quantities determine the extent to which hydrogen ion will unite with
negative ions. For example, the statement that the concentrations of hydrogen ion and hydroxide ion in pure water are 10~~7 moles per liter is equivalent to saying that the 2 O, takes place until the concenreaction, H+ + OH~ = trations of the ions reach this value. Likewise the statement that the volatility of hydrogen chloride from its water
solution
reaction,
is
high at 100 C. is equivalent to saying that the 4 + Cl~ = HC1 (gas), has a strong tendency
"
to take place at this temperature. 7. Many of the most important reactions of hydrogen ion and hydrogen gas may be summarized in terms of the
4 e~. (The electron oxidation-reduction couple, ^H2 = will be denoted by a dot in certain structural formulas, as
"
H +
in
Paragraph
5,
but
in writing
ordinary equations,
we
will
use the symbol
For example, zinc will displace or e~.) liberate hydrogen from acids because the reaction, Zn
pressure*' (voltage) of gives a higher 2H + = Zn ++ electrons. The total reaction, Zn is 2 the result of the transfer of the electrons from the zinc to
1
= Zn 4" +
"
"
2e~,
+H
the hydrogen ion. On the other hand, the reaction Ag = Ag 4 + e~ has a lower voltage than hydrogen; and hy= 2Ag 2 2H+, by drogen reduces silver ion, 2Ag+ the transfer of electrons from the hydrogen to the silver ion. Reference may be made to the table of oxidationreduction potentials (Append. II) for the position of hydrogen in respect to a large number of oxidation-reduction
"
+H
couples. Mention should be made of the fact that the oxidation of metals by hydrogen ion is often a slow reaction,
and that the speed depends greatly upon the nature of the surface upon which the gas deposits. Thus the action of acid upon zinc proceeds very slowly if the zinc is pure, and rapidly only when impurities are present. The power of
8]
HYDROGEN
its
Hydrogen ion as an oxidizing agent depends, of course, upon concentration. In normal alkaline solution, a stronger reducing agent is required to liberate hydrogen than in acid
= 2 since the potential of the reaction, iH 2 e~, is 0.83 volt more positive than the potential of the
+ OH~
HO
acid couple.
Although the formula of hydrogen ion

+ is written as H
,
in
water solution
the ion exerts such a strong attraction upon the water molecules that it might be written H(H 2 O) n +. The energy of hydration of the hydrogen ion, approxi-
mately 250,000 charged ion.
cal., is
larger than that of
any other
singly
8. Preparation. Although hydrogen is liberated by the action of the electropositive metals, such as sodium, potassium, and calcium upon water, these metals are too ex-
pensive for its practical preparation. Hydrogen is sometimes prepared by passing steam over finely divided iron heated to redness. 3Fe + 4H 2 O = Fe 3 O4 + 4H 2 The gas is conveniently prepared in the laboratory by the action of
.
dilute sulfuric or hydrochloric acid upon zinc or aluminum. Hydrogen so prepared usually contains small quantities of
volatile
of impurities in the metals.
hydrogen compounds resulting from the presence These may be removed by
bubbling the gas through a permanganate solution. Water vapor is conveniently removed by contact with concentrated sulfuric acid.
There are four principal sources of commercial hydrogen the reduction of water by carbon, the destructive distilla? tion of coal, the cracking of methane CH*, and the electrolysis pt aqueous solutions. The reduction of water by carbon involves the water gas reaction: H 2 O + C = CO + H 2 and the further reaction, H 2 O + CO = H 2 + CO2 (cf. XIII 6). Coke-oven hydrogen is a by-product of the destructive distillation of coal and contains large quantities of methane, which may be removed by liquefaction. Elec:
r<
trolytic
hydrogen
is
now usually prepared by the electrolysis
10
REFERENCE
[Ch.
sodium hydroxide solutions with iron or Hydrogen is liberated at the cathode and at the anode. The gas is quite pure except for a oxygen small quantity of oxygen which is present by diffusion from the anode. This may be removed by passing the gas over a catalyst, e.g. finely divided nickel at 250 C., which accelerates the combinations of hydrogen and oxygen. Large quantities of hydrogen are also formed as a by-product in the manufacture of sodium hydroxide (cf. IV 12) by the
of concentrated
nickel electrodes.
electrolysis of salt brine.
Commercial Uses. The_ oxy-hydrogen^Jiame is used The temperatureToFthe in cutting and welding metals. "flame is approximately 2,500 C. A special burner is employed which prevents trie explosion of the gases by mixing them just before they reach the orifice. The atomic hydro9.
gen torch, recently developed, has many advantages in welding under reducing conditions. The atomic hydrogen is formed by blowing hydrogen through a very hot electric arc. The metal surface acts as a catalyst for the union of the atomic hydrogen and is heated to a high temperature, estimated between 4,000 and 5,000 C., by the heat liberated
through the formation of the H 2 molecule. Large quantities of hydrogen are consumed
facture of
in the
manu-
s>^hetic^mfaonkt by the
direct union of the
elements, 'fhe synthetic production of methanol, 3 and other liquid fuels by the reaction of hydrogen Ifnxf car
CH OH
bon monoxide
in the presence of catalysts
promises to be
come
seed
of great industrial significance. use is in the hydrogenation of many

oil,
Another importan
oils,
such as cotton
to form solid fats.

is
Hydrogen
loons.
also
Its efficiency
of equal liter at
volumes of C. and 1 atmosphere.
employed as a lifting medium in bal depends upon the difference in weigh hydrogen and air. This is 1.2 grams pei
Hydrogen is often determined by mix ing with an excess of oxygen and passing the mixture over a
10. Analytical.
11)
HYDROGEN
11
glowing filament electrically heated. The per cent of hydrogen is calculated by the contraction in volume due to the formation of water. Hydrogen is also determined by passing the gas over hot copper oxide, CuO + H 2 = Cu + H 2 O, and absorbing the water in a weighed tube of calcium
chloride.
Deuterium. Since the mass of deuterium is approximately double that of ordinary hydrogen, its nucleus may be considered to be composed of one proton and one neutron. The resulting charge is one positive so the atom has but one "orbital" electron. The electron energy levels are almost identical with those of the mass one isotope and the principal differences in the physical and chemical properties of the two isotopes are due to the difference in the energy of vibration of the two atoms in their various molecules. For
11.
example, the energ^ôf dissociation^ of D 2 is LSJ^QaLJarger than that of H 2 because of the difference in energy of the vibrational states. Similar differences in the energies of the bonds of hydrogen and deuterium to oxygen exist in the oxides H 2 O and D 2 O. The heat of vaporization of D 2 O j^ about 260 cal. per mole greater than that of H 2 0.
,
TABLE
Atomic weight
Boiling point Freezing point
II
PHYSICAL CONSTANTS OF DEUTERIUM AND HEAVY
WATER
1.1066
3.82 101.42
11.6
.
02 = 2D+
-f 2e~
D D D
2,
2.00147
2,
A. A.
.
23.5
18.7
Density D 2 25 C. ... Melting point D 2 O C. Boiling point D 2 O C.

.
(in
pure D2O)
0.0046
Temperature of maximum
(volts)
D O = OD- + D+ K 26
2
density,
0.3
1Q-"
jfrhe preparation of pure deuterium was first carried out b^-the fractional electrolysis of a sodium hydroxide solution with nickel electrodes%lpie hydrogen evolved at the cathode is 5 to 8 times poorer in deuterium than the water and the heavier isotope thus accumulates in the residues.
12
REFERENCE
[Ch.
Concentration of DH and D2 in liquid hydrogen may also be effected in an efficient distilling column\ The replacement of hydrogen atoms by deuterium in organic molecules has opened many new fields of investigation into the
actions.
12. Tritium.
mechanism
of organic
and biochemical
re-
The mass
.
three isotopes has a half-life of
J8 (electron" emission) disto form He 3 The /3-electron is soft, having an integration energy of onlyÔ.018 Mev^ It may be formed from deu-
124 vears with respect to the
terium by a slow neutron capture,
H +
2
H +7
3
and by a number
elements such
as,
of nuclear reactions involving the lighter
H +H =H +H N +n=C +H
2
14
12
The
probably accounts for most of the very small amounts of H 3 and He 3 found in the atmosphere. The neutrons required for the reaction are generated by cosmic radiation. It is estimated that this source produces 0.8 neutrons per second per cm 2 of earth's surface. Tritium, as well as deuterium, has become most useful
latter reaction in studying the
and
3
its
mechanism of reactions involving hydrogen compounds. In this case, the radioactivity of the
be used to follow the course of the reaction. The of liquid tritium at 20.4 K. is estimated
H may
vapor pressure to be 45 mm.
Chapter
II
INERT GASES: HELIUM,

As early as a small amount
1.
NEON, ARGON, KRYPTON, XENON, RADON

1784, Cavendish
of
showed that air contained an unknown gas which was quite nonreactive, but further work on the subject was not published until 1893, when Lord Rayleigh found that the weight of 1 liter of nitrogen prepared from pure nitrogen compounds was 1.2506 g., as compared to 1.2572 g. for
atmospheric nitrogen. This discrepancy led to a careful investigation of atmospheric nitrogen by Rayleigh and
to the discovery of argon. Ramsey shortly after identified the gas given off by uranium minerals as
Ramsey and
the
unknown element,
had postulated
in 1868 to
helium, whose existence Lockyer account for a prominent yellow
line in the solar spectrum. Subsequent investigation by fractional distillation of the crude argon obtained from air led to the discovery of neon, krypton, and xenon, the percentage by volume of the various gases in air being
:
natural gas fields of Texas and Kansas contain amounts, a number of these wells, high in nitrogen content, analyzing between 1 and 2 per cent of the
The
helium
in small
gas.
Research on the radioactive elements (Chap. XXII) has

13
14
REFERENCE
[Ch.
II
so-called alpha-ray, or particle, is doubly helium, and that helium is thus one of the products charged of the decomposition of these unstable elements. It has been calculated that a gram of radium produces 0.11 cc. of
shown that the
helium per year, and a gram of uranium oxide, UsOg, 9.1 X 10~8 cc. The radioactive mineral monazite contains about 1 cc. of helium per gram. The loss of an alpha particle by radium results in the formation of the heaviest member
of the inert gas group, radon, also called niton (Chap. XXII). 40 40 and this is the product of the /3-decay of Argon,
accounts for the greater abundance of argon. The more important physical 2. Physical Properties. properties have been summarized in Table I. The gases are all monatomic, and the low values of the boiling points indicate that their atoms have very little attraction for each other. Indeed, the helium atom is so inert that this element possesses the lowest boiling point of any substance, and by boiling under reduced pressure (below 0.01 mm.), a Solid temperature of 0.7 absolute has been obtained. Considerable pressure (140 atm. at 4.2) is required to cause liquid helium to solidify and the force of atVapor traction is so small that the 2.2 heat of solidification at the Temperature, K FIG. 1. Diagrammatic representation lowest temperatures is pracof die phases in helium at low temperat}ca j ly Q hydrogen, helium gas heats slightly when expanded at ordinary temperature and the gas must be cooled to the temperature of solid hydrogen (about 11 A.) before it can be cooled by free expansion. When liquid helium is cooled to 2.2 A. a remarkable
u^
transition occurs, for example, the viscosity decreases and the thermal conductivity increases. The substance seems
W 3 J 531
-JJ
15
16
REFERENCE
[Ch.
II
to be a solid with properties of a gas. This appears to be a different state of matter and it is referred to as a degenerate
gas.
The phase relations are indicated in Fig. The helium isotope of mass three which
1.
is
present in
7 atmospheric helium to one part in 10 (cf. I 12) has a It does not appear to have the boiling point of 3.2 K.
degenerate liquid II phase. The inert gases are somewhat soluble in water and the solubility increases markedly with increasing atomic weight. Helium and neon are not appreciably absorbed by charcoal cooled in liquid air, but the heavier gases are readily
absorbed.
various gases under the influence of a high voltage discharge are luminous, due to the light emitted upon the recombination of the electron with the atom, and the characteristic spectrum of each of the elements, thus produced, serves as a ready means of identification. 3. Electron Structure and Chemical Properties. The of the electrons in the various atoms of the configuration
The
group is important, not only as explaining their inertness, but also in connection with the interpretation of the formation of the great majority of chemical compounds. Each marks the completion of an outer shell of eight electrons, except in the case of helium which completes the
inert gas
first quantum group containing but two electrons (Table I). These completed groups are so stable that not only are the ionization potentials of the inert gases very high, but the elements preceding and following each inert gas readily gain or lose sufficient electrons to form ions with the same electronic structure, i.e. the completed octet. This is illustrated by the following ions all with the electron structure of neon
:
4]
INERT GASES
of
17
Thus the formation
many
binary compounds consists
from a metallic element to a non-metallic element with the formation of positive and
in the transfer of electrons
negative ions of the inert gas type,
e.g. in
the ions
above:
Na + F = (Na+ )(F~), and

lattices built
pounds are
up
crystals of such of these ions (cf. Append.

it is
shown com-
V for
many
all
lattice types).
However,
not to be inferred that
positive ions are of the inert gas type, as most of the noble metals form ions of somewhat different structure
(cf.
VII
1).
Although the statement is generally made that the inert gases form no compounds, a few relatively unstable compounds do exist. Thus helium and hydrogen gases subjected to an electrical discharge contain small amounts of the ions, HeH + and HeH 2+ and the large solubility of the heavier
,
members
of the group indicates the formation of unstable hydrates. It is claimed that under a pressure of 15 atmospheres at 0, krypton forms the hydrate, Kr-5H 2 O.
series of
compounds,
stable
below
130, has been

e.g.
re-
ported for argon and boron trifluoride,
A(BF 3 ), A(BFa)2,
A(BF 3 )
4.
6.
Commercial Preparation and Uses. The United States government operates a plant in Texas for the extraction of helium from natural gas. During the period 1929
to 1937 approximately eighty million cubic feet of the gas were extracted. The process is one of fractional liquefaction. The gas is usgdjn dirigibles and balloons as it has a lifting power only aboufÎCTpier "cent fess than hydrogen and
is,
of course, non-combustible.
considerable importance in deep diving and in deep caisson operations, where men engaged are subject to ^caisson^diseas&.ll^This is due to the solution of nitrogen in tli^blood at high pressure, and its subsequent escape when the pressure is lowered, forming bubbles in the capillaries, or in the brain or spinal cord. It has been shown
"Helium has assumed
that the time required in coming out from under high
18
REFERENCE
is

by the substitution
air,
[Ch,
II
pressure
of
greatly reduced
for
of a mixture
on account of the compressed of helium. Mixtures of helium and oxygen small solubility are also used in treatment oT acute cases of asthma and other diseases where there is constriction of the air pasoxygen and helium
sages.
*"
boiling point of helium makes it of special importance in the investigation of the behavior of substances in the neighborhood of absolute zero. Among the
The very low
more
significant changes at these temperatures is the disappearance of the specific heat and coefficient of expansion
many metals. the resistance of metals decreases Although, with decreasing temperature, there is often an abrupt drop a few degrees above absolute zero: thus, at 7 A., the resistance of lead suddenly decreases a million-fold.
of solids,
in general,
and the
electrical resistance of
The neon tubes used in electric signs contain the gas under low pressure. The commercial source of the element
the fractionation of atmospheric argon. Argon is now used extensively in filling electric light globes. The presence of the inert gas decreases the rate of evaporation of the filament, retards the blackening of the bulb, and makes possible the operation of the lamp at a higher temperature, thus greatly increasing its efficiency.
is
Argon and
atmosphere
also helium are

in
employed to provide an inert welding magnesium and aluminum.
Chapter
III
OXYGEN
Group VI, oxygen, O, sulfur, S, selenium, Se, and tellurium, Te, are characterized by the presence of six outer or valence electrons, and the tendency to complete the octet of the noble gas structure by the addi1.
The elements
of
Consequently these elements readily form compounds which they have an oxidation state 2. This tendency is the greatest with the smallest of atom; hence oxygen is the strongest oxidizing agentând
tion of
electrons.
in
two
On the other hand the six valen :e atom may be removed, wholly or in part, giving positive oxidation states up to six. In the case of oxygen this can only be done by high potentials in the
tellurium the weakest,. eTectrons of the neutral
gas at low pressure, as no other element is capable of removing electrons from oxygen; hence no ordinary compounds exist in which the oxygen atom must be considered as having a positive charge (with possible exception of F2 O). This separates it considerably in chemical behavior from the other members of the group, and suggests its separate consideration.
2. Occurrence. Approximately half by weight of the material of the earth's crust is oxygen, and since the atomic
weight of oxygen
is less than the average atomic weights of the other elements, it follows that more than half of all the atoms of the earth's crust are oxygen. The most abvwxdaQJ of its_compounds are those with silicon and aluminiUKL Tfie element "occurs 7n the free state in the atmosphere,
19
20
REFERENCE
[Ch.
Ill
which is one fifth oxygen by volume. Eight ninths by weight of water and between 40 and 50 per cent of all rocks is oxygen. Compounds are known with all the elements except
the noble gases.
Physical Properties. In common with the other eleof the family, oxygen exists in several molecular forms. In the gaseous state there are two modifications,
3.
ments
ordinary oxygen, O 2 and ozone, O 3 These and probably O 4 also can exist as liquids. Solid oxygen exists in at least ffifee mocTrfications. TKeTmore important properties of the
, .
oxygen atom and the 62 molecule are given
in
Table
I.
TABLE
Atomic number
i *j INUCIeus /
ATOMIC AND PHYSICAL PROPERTIES OF OXYGEN

neutrons
8 8 8 16.00 16
Density
g.
1
per cc.
At.,
C.
and
gas
liquid
\ protons
(+ )
Atomic weight
Isotopes traces of 17 and 18 Electrons in various energy
levels, 1st
0.0014290
183
at
1
1.13
Vaporization
At.
90.1
Temperature
2
Heat, cals Fusion
1629
2d
lonization potential, volts 1st electron 2nd electron Electron affinity, volts 1st electron 2nd electron Heat of dissociation of O2 molecule, kcal Dielectric constant of liquid. Magnetic moment of liquid O 2 compared to iron as
6
13.55 34.93
2.2
Temperature
Heat, cals Transition Solidi
A
=
Solid2
54.4 105
Temperature
Heat, cals Transition Solid2
A
=
Solids
43.7 177
23.7 17.5
9.5
Temperature
Heat, cals Solubility per 100
25 100
A
g.
117.3
1.47
water
0.007 0.004 0.001
C C C
unity
0.001
crystals,
Radius of O" in cm. X 10*
1.40
The oxygen molecule O 2

this
is
highly magnetic, and since
property
is
associated with
it
atoms having an odd num:
ber of electrons,
for the
is
:
:
assumed that the electron formula

*
:
molecule
is
O O
rather than
O O
: :
or
O O
:
5]
OXYGEN
21
The variation with concentration of certain of the properties

oxygen dissolved in liquid nitrogen may be exon the assumption of an equilibrium, 2O* = O4 plained The change of this equilibrium with temperature may exof liquid
.
plain the very large coefficient of expansion of the liquid. In harmony with the assumed structure of C>2 the most
likely structure of C>4
would be
:O :O :O :O
However the small energy of formation of O4 suggests that the bonds between the two O% molecules are not true electron pair bonds.
Chemical Properties. Oxygen combines directly with other elements except the halogens, the noble gases, and a few of the most noble metals, and in many of these reactions sufficient energy is evolved to heat the products to
4.
all
carbon in
the point of incandescence, as in the familiar burning of air. Very often reactions of oxygen which are
rapid at high temperatures will not proceed at low temperatures; thus carbon must be keated before it ignites in air,
but
many oxidations do go slowly in the coM, e.g.

of
the rusting
is
of iron.
A compound
oxygen with another element
called an
2 (except in peroxides, oxide, and the oxidation state of Par. 11) is assigned to the oxygen indicating that it has
gained two electrons,
e.g^
2Ca
+ 6 6 =
:
:
2Ca
6. The slowness of many oxygen reactions is doubtless connected with the large energy required to dissociate the oxygen molecule into atoms. Indeed the probable mecha-
nism of most reactions of oxygen
is first
electrons to the Og to form a peroxide, where the
the addition of two bond be-
22
REFERENCE
[Ch,
III
tween the oxygen atoms remains unbroken, as illustrated

by:
Ba
6 + O =
:
,
_ Ba
6 -
:O
process of oxidation may be examined in detail by arbitrarily dividing the formation of an oxide into the following steps. (This does not imply that the process of oxidation ordinarily occurs in this way.) Using copper oxide by way of
illustration
:
The
2 (gas)
a b -> O(gas) ->
Q- 2 (gas)
Cu(solid)
>
Cu(liquid)
>
Cu(gas)
>
Cu+^gas)
The
dissociation of the oxygen molecule, step a, involves the absorption of a large amount of energy, as do also steps c and d which represents the detachment of copper atoms from the solid mass. The removal of electrons from the
y
metal, step e, requires the absorption of still more energy The addition of two elec(i.e. the ionization potential).
trons to the oxygen atom, step b
also requires energy; although it is not large, because of the tendency to complete the octet. It is step/ which is chiefly responsible for making the net result of the whole process an evolution of
y
energy, and this step must be very large in order to overcome the energy absorption of steps a, &, c, d, and e. Now it is very illuminating to note that step / depends for positive ions of the same charge chiefly upon the size of the
ions,
being greater the smaller the positive ion. Furthermore, the great stability of oxides, as compared with many other binary compounds, depends upon the fact that the oxygen ion is one of the smallest negative ions. The effect of step /, for example, makes the heat of formation of lithiu/Ti oxide, 142 kcal., greater than that of sodium oxide,
6j
OXYGEN
in
101 kcal., in spite of the fact that more energy is absorbed removing the electron from lithium than from sodium.
The above scheme throws

heat of combustion
light upon differences in the of other substances. Thus a metal of
high melting and boiling point, such as platinum, owes its noble character in part to high values for steps c and d, and not entirely to a high value for step e. Again, the high stability of silicon dioxide is related to the large energy evolution of step /, which may be inferred from its high melting point and great hardness. Commercial oxygen is now 6. Preparation and Uses. the fractional distillation of prepared on a large scale by liquid air. The principle of the method may be understood
by considering the
tions of oxygen
and
liquid vapor diagram, Fig. nitro92
1,
for solu-
Nitrogen boils at gen. 195 C. and oxygen at - 183 C. At intermediate

temperatures, a solution of the two liquids in equilibrium with the vapors has the composition b and the vapor, the composition a.
Since the gas phase is much richer in nitrogen than the
1 88
S84
f 1 80
76,
20
1.
40
60
80
100
Per cent of Oxygen
FIG.
Temperature-composition dianitrogen.
gram for liquid oxygen and
liquid, evaporation results in the liquid becoming richer in oxygen.

off
Simply boiling
the nitrogen from liquid air would not give an efficient separation of the two gases, so the process is carried out in a fractionating column. The cold liquid enters the top of the column; as the liquid evaporates the
temperature rises and the liquid increases in oxygen content; the vaporized gas passes up through the colder liquid and loses oxygen, becoming almost pure nitrogen. Oxygen cannot be liquefied above its critical temperature, 118 C., by any pressure, however great; but the fact
24
REFERENCE
[Ch.
Ill
that compressed air at room temperature cools upon expanding, due to the work done in overcoming the attraction
between the molecules (Joule-Thomson effect), makes possible the Linde liquefaction process. Air is compressed to about 3,000 Ib. per sq. in. and allowed to expand. The cool expanded air is led back over the incoming highly compressed air and cools it until finally the temperature drops sufficiently below the critical temperature to permit liquefaction. In the Claude process the compressed air is subjected to an additional cooling effect by doing external work. Some commercial oxygen is prepared by the electrolysis of water; however, unless the electrical energy is very cheap and there exists a ready market for the hydrogen produced at the same time, the electrolytic process cannot compete with the liquid air process. Barium peroxide was formerly an important source of
oxygen, since the reaction,

reversible.
BaO +
vO% = BaC>2,
is
easily
The
process was usually
carried out at 700
C.
the barium peroxide being first formed from air at a pressure of about 3 atmospheres, and the oxygen then pumped
off
by reducing the pressure. Sodium peroxide (cf. IV-11)
is
a convenient source of
common laboratory method oxygen in small quantities. for the preparation of oxygen consists of the decomposition
of potassium chlorate using manganese dioxide as a catalyst 3O 2 In the absence at about 200 C.: 2KC1O 3 = 2KC1
of a catalyst, oxygen is evolved but slowly; most of the chlorate being converted into perchlorate, which is much more stable. In the early investigations of oxygen by
Scheele, Priestley, and Lavoisier (about 1775) much use was made of the compounds HgO, PbO 2 and 2 3
MnO
KNO
all
which give oxygen upon heating. The present commercial importance of oxygen has resulted from the development of the oxy-acetylene torch in welding and cutting metals. Oxygen for this purpose is sold in heavy cylinders under a pressure of about 2,000 Ib.
of
7]
OXYGEN
25
per sq. inch. The oxy-hydrogen torch, although not producing as high a temperature as the oxy-acetylene flame, is also of wide industrial use. Pure oxygen is used in the treatment of pneumonia and in cases of asphyxiation and mixtures of oxygen with nitrous oxide or ether are administered in producing anesthesia. It is also used to maintain the oxygen content of the air in submarines. The "harden;
ing" of certain oils is accelerated by using pure oxygen. Charcoal, cotton, or other cellulose soaked in liquid oxygen
form high explosives known as "oxylignite."

Oxides, Bases, Acids. The various types of oxides with different elements correspond to all the possible oxidation states of the positive elements from + 1, as in Cu 2 O, to + 8, as in OsO 4 In addition, a number of mixed oxides occur with elements forming oxides of more than one state,
7.
.
example Pb 3 O 4 which is (PbO) 2 PbO 2 and Fe 3 O 4 which FeO-Fe 2 O 3 In the crystalline state, if the force of attraction between the positive kernel and the oxide ion is not
for
,
,
is
too great, the oxides crystallize in the completely polar type of structure: for example, the CaO crystal is a lattice of Ca ++ and O similar to the sodium chloride structure, and
the other hand, large attractive forces allow the molecule to preserve its identity in the solid as in carbon dioxide.
there are no molecules of CaO.
On
Oxides of metal ions with small positive charge react with water to form bases, e.g. Na 2 O + H 2 O = 2NaOH,
MgO + H O = Mg(OH)
2
while oxides of non-metals, and
even of metals in the higher oxidation states react with water to form acids: e.g. C1 2 O + H 2 O = 2HOC1; SO 2
+H
H S0
2
.
CrO 3
+ H O = H CrO
2
In all of these 3 4 separates a hydrogen atom from the remainder of the molecule; and the basic or acidic character seems to depend
= 2H AsO
As 2 O 6 + 3H 2 O compounds an atom of oxygen

2
4
;
largely upon the relative attractive forces between the oxide ion and the hydrogen ion, on the one hand, and the re-
mainder of the molecule on the other, modified by the
26
REFERENCE
[Ch.
II!
energy of hydration of the resulting ions. Thus NaOH is a base because the cleavage occurs more easily at a, while HOC1 is an acid because it occurs at b.
Na
:
|
:
|
Cl
:
|
:
|
The bond between the sodium and oxygen is largely that of the coulombic attraction [E = ee'/(r r')], while the bond between the chlorine and oxygen has considerable
covalent (electron pair) character. The greater ability of the chlorine to take electrons away from the oxygen makes the latter more positive in HC10 than in NaOH and, in
general, the
its
more positive the oxygen the weaker bond with the hydrogen.
will
be
The strength of the oxygen acids may be correlated with the formal charge on the central atom which is calculated on the assumption that the electrons in the bond are divided
equally between the two atoms.
Thus
as seen in the for-
mula
of
HC1O,
this
assumption would give seven electrons
Cl
6 Cl 6 ......
: :
6 Cl 6 H ......
:
:
:
Formal Charge
Formal Charge
4- 1
Formal Charge
on the chlorine and
since the neutral
atom has seven
elec-
trons, the formal charge is zero. Oxygen acids with zero formal charge are very weak and have dissociation constants, Ki, of 10-' or less (cf.
If
Table
II).
the formal charge on the central atom is 1, as in HC1O 2 illustrated above, Ki is approximately 10~2 As a general rule the difference between successive dissociation constants is roughly 10~"5 hence J 2 for this class of acids is 1(T7 and KT12 Acids with a formal charge of 3 2 are strong. Ki is probably 103 and K* KT2 There are two acids with formal charge of 3, H.C1O 4 and 4 Both are very strong.
.
K ~
HMnO
9]
OXYGEN
TABLE
II
CORRELATION OF ACID DISSOCIATION CONSTANTS WITH FORMAL CHARGE
The effect of the formal charge may be interpreted as an increased displacement of the electrons toward the central atom with increasing charge and this in turn weakens
the hydrogen-oxygen bond. In some acid3 there is partial double bond character. This is true in H 2 CO 3 and the 1 in this acid. and formal charge is between Both oxygen and nitrous oxide 8. Analytical Properties. will cause a glowing splinter to burst into flame, but oxygen may be distinguished from the latter by the production of
dark brown fumes with nitric oxide. The gas is usually determined quantitatively in a mixture of gases by determining the decrease in volume upon contact with various liquids or solids which absorb oxygen, such as, (1) a solution
of cuprous chloride in hydrochloric acid, (2) alkaline solution of pyrogallol, (3) phosphorus. very delicate test for small quantities of oxygen is the deep red color produced
by the
9.
action of oxygen upon an alkaline solution containing
ferrous iron
and pyrocatechol.
Water.
Water plays such an important
role in
chem-
istry that its physical constants are of especial significance. For a substance of low molecular weight, its melting point,
boiling point, 100 C, are extremely high, indicating high attractive forces between the molecules. The high dielectric constant, 81 at 18 C., shows that the mole-
C, and
cules are highly polar, which would account for the large intermolecular attraction, since two dipoles would attract
REFERENCE
[Ch.
Ill
each other. The unusual solvent action of water for salts is also to be correlated with its high dielectric constant,
since the force of attraction
between ions varies inversely

as the dielectric constant of
the medium.
Water
is
un-
usual in possessing a point, C., of maximum density
(Append. VIII). This may be connected with the fact that water is one of the few substances whose liquid form (d = 1.00 at 4 C.) is denser than the solid
In ice the 0.917). molecules are combined in a way that involves a looser
(d
FIG.
2.
Arrangement of water molecules in ice.
packing than in the liquid (cf. Fig. 2), and as the tem-
perature of the liquid approaches 0, there are doubtless formed an increasing proportion of these same molecules in the liquid. This change
counteracts the increase in
density uniformly found when only one molecular

species
is
Liquid
present.
Complete
Solid
vapor pressure tables for water and ice are given in
4.68 O.OG7
Appendix X. The simple " solid, phase diagram for " liquid, vapor is represented
in Fig. 3. Since the density of the solid is less than that
-10
5
Vapor
Temperature,
of
the liquid, the melting point is decreased by pressure.
FIG.
3.
gram
for ice, water,
Temperature-pressure diaand vapor.
At high
pressures ice exists in a
number
of allotropic
modifications,
and as several of these are denser than the
9]
OXYGEN
29
they may be obtained under high pressure at temperatures above 0, as shown in Fig. 4. The water molecule may be considered as a tetrahedral oxygen with hydrogens attached to two corners. However
liquid,
the angle is only 105 in the gas instead of the tetra-
hedral
109 28'. Crystal structure data inangle,
2
x
10
Ice VI
dicate that in the ordinary
i
1.
form of ice each oxygen atom is surrounded by four other oxygen atoms with a hydrogen atom located on
the line joining the oxygens, thus forming a hydrogen
\
Liquid
Icel
Ya
80
-60
40
-20
20
40
bond between the oxygens.
Temperature
The heat of fusion is 80 cal. per gram and the heat
FIG. 4. Modifications of ice at high

pressures.
The lowering of the of vaporization, 540 cal. per gram. of boiling point per mole freezing point and the elevation of solute in 1,000 g. of water
are 1.86
tively.
and 0.52
The lowering
salt is
respecof the
freezing point of water by
common
important
in
refrigeration.
The
is
freezing
point diagram
Fig. 3,
given
in
Chapter IV.
One
of
the lowest eutectics given with water is that of CaQ 2 Temperature (not
to scale)
FIG. 5. Diagrammatic representation of the effect of a solute upon the vapor

pressure, boiling point of water.
point,
6H 2 O. A
of
mixture of 7 parts
and melting
snow and 10 parts of CaCl 2 -6H 2 O gives a tem-
55 C. (cf. perature of tension of water at 20 Fig. 2, Chap. V). The surface is 72.5 dynes per cm. The compressibility at 20 is
30
REFERENCE
[Ch.
Ill
43 X 10~6 cc. per megabar. The specific heat of 1 g. of water at 15 is taken as unity in the definition of the calorie. The variation of its specific heat with temperature
is
1.0099.
0, 1.0088; 30, 0.9988; 50, 0.9996; 100, The heat of formation per mole of H 2 O at 25 is - 68,270 cal. The heat of ionization, H ? O = H + + OH~,
as follows:
is
13,200 cal.
of course the negative of the heat of neu-
tralization of dilute solutions of strong acids and bases. The constant for a first ionization of water is 1.008 X 10~ 14 at
C. and the constant for the second ionization probably than 10~ 36 The decomposition voltage of water upon electrolysis is 1.23 volts plus an overvoltage depending upon the nature of the electrodes due to the slowness of the electrode reactions (cf. Append. I). The specific conductiv7 ity of the purest water at 20 C. is about 1 X 10~ reciprocal
25
less
ohms.
10.
Water
is
;
by
distillation
easily purified trom non-volatile substances however, to prepare water free from volatile
and organic material, elaborate precautions must be taken. This is usually done by first distilling from an alkaline solution of permanganate to remove organic material and volatile acids, especially carbonic, and then redistilling from non-volatile acid solution to remove volatile
acids, bases,
alkalies, especially ammonium. If the vapor is condensed in air it will contain dissolved gases, hence the distillation is carried out in vacuum. Due to the solubility of glass in
water, the condenser

so-called "softening
is
made
of quartz, tin, or silver.

is
The
of
hard water"
discussed
under
calcium
11.
(cf.
11).
Hydrogen Peroxide. The formation of peroxides as intermediate products in the direct oxidation by oxygen has been mentioned (Par. 4). These compounds may be considered as derivatives of hydrogen peroxide, The 2O 2 oxidation state of the oxygen is 1. In terms of molecular
structure peroxides consist of oxygen linked to oxygen to

.
form the group
O O
:
12]
OXYGEN
31
The
in the
oxidation of certain metals by moist oxygen results formation of the oxide and hydrogen peroxide: e.g.
Zn
O2
+ H2O = ZnO + H O
2
2.
The mechanism
of this
its
reaction
may
be the formation of zinc peroxide and
sub-
sequent hydrolysis.
the action of
Hydrogen peroxide is also formed by ultraviolet light upon water: 2H 2 O = H 2 O2
High anodic potentials are capable of oxidizing the oxygen in many of its compounds to the peroxide state:
2.
+H
for example, concentrated sulfuric acid is oxidized to per-
oxydisulfuric acid
O O HOSOOSOH.
This acid
may
then be
hydrolyzed to form hydrogen peroxide and sulfuric acid. Some commercial hydrogen peroxide is prepared in this manner, but the greater portion is prepared by the action
of
cold
sulfuric
acid
upon hydrated barium peroxide:
The peroxide being less 2 2 be concentrated by evaporation under reduced pressure. Another method of preparation involves the formation of hydrogen peroxide as the product of the oxidation of organic hydrazo-compounds by oxygen. The hydrogen peroxide is removed by distillation and the hydrazo-compound regenerated by reduction with sodium.
BaO 2 + H 2 SO 4 = BaSO 4 volatile than water may
+HO
amalgam. 12. Pure hydrogen peroxide is a faint blue syrupy liquid 2. It has a vapor pressure of 47 mm. at freezing at 80 C. Violent decomposition occurs if heated much above
this temperature.
The
dielectric constant of the liquid is
given as 93, a value even higher than that of water. The water solutions are fairly stable if kept in a cool, dark place.
Acetanilid
usually added to the commercial product to act as a preservative. The decomposition into water and = 2O O 2 is catalyzed by many sub2O 2 oxygen,
is
stances, for example, silver,
manganese
dioxide,
is
bromide, and saliva.

alkaline solution.
The decomposition
hydrogen more rapid in
The
usual 3 per cent commercial prepara-
32
REFERENCE
[Ch.
Ill
tion is often called a "10 volume solution" since it will evolve about 10 times its volume of oxygen. Peroxide is a powerful oxidizing agent in both acid and alkaline solutions (Par. 14), the oxygen being reduced from 1 to 2. However, it is generally an oxidation state of
a slow oxidizing agent except with fairly powerful reducing agents. One of the most important reactions of hydrogen peroxide is the quantitative oxidation of iodide: 2I~ + H 2 O 2 + 2H+ = I 2 + 2H 2O. It also acts as a reducing agent, the 1 to 0, but a fairly powerful oxygen being oxidized from is required to bring about its oxidation in oxidizing agent acid solution. As examples we have the quantitative reduc~ tion of permanganate: 5H 2 O 2 + 2MnO 4 + 6H+ = 2Mn++ + SO 2 + 8H 2 O, and the reduction of silver oxide: Ag 2 O
+HO =
2
2Ag + O 2 Hydrogen peroxide

2
+H
is
O. used as an antiseptic and as a

2
bleaching agent for hair, silk, feathers, ivory, etc. Delicate qualitative tests for peroxide are the reactions
with chromate or titanic sulfate
acid, forming highly colored peroxy-acids. The peroxychromic acid is a bright blue compound, soluble in ether, and the peroxy titanic
in
acid
is
yellow.
There are a large number of acids These may be considered as containing peroxy-oxygen. derivatives of oxy-acids formed by the substitution of
13.
Peroxy-acids.
OOH in place of OH~,

OOH
CO
for
example
OOH
CO
OOH
CH C
3
\ OH
\ OOH
\O
monoperoxycarbonic
diperoxycarbonic
peroxyacetic
The elements forming
peroxy-acids are B, C, Ti, Ge, Sn, N, P, V, Cb, Ta, S, Cr, Se, Mo, W, and U. Many of these acids are discussed under the respective elements. The most
is
important
probably peroxydisulfuric acid,
S 2O8
14]
OXYGEN
33
14. Ozone. The density of ozone corresponds to the The reaction, 3O 2 = 2O 3 absorbs molecular formula O 3 34.5 kcal. per mole, and the formation of ozone from oxygen is therefore favored by high temperature. The equilibrium mixture of the gas at 3,000 C. probably contains about one per cent of ozone. Sufficient energy to bring about the transformation may be supplied either by ultraviolet radiation or by a silent electrical discharge. The commercial ozonizers
.
,
usually consist of aluminum plates, separated by insulators, and charged to a potential of about 10,000 volts. When oxygen is passed over the plates, a few per cent of ozone is
Ultraviolet radiation of about 2,600 A. (corresponding to 4.7 volts) is absorbed by oxygen molecules. These highly activated molecules then react to form ozone.
formed.
The
outer portion of the earth 's atmosphere must contain large concentrations of ozone formed in this manner by the sun's radiation. The silent electrical discharge is the principal commercial means of forming ozone. This involves the
action of electrons shot off from high-potential surfaces upon oxygen molecules. Ozone is also formed under powerful oxidizing conditions, as in the action of fluorine
upon
water, and
water by a high anodic potential, as, for example, in the electrolysis of aqueous sulThe ozone furic acid using a very high current density. molecule appears to be V-shaped and not a triangular ring
by the oxidation
of
as previously postulated. Reference to the table of oxidation reduction potentials
shows that ozone
is itself a very powerful oxidizing agent, second only to fluorine. In the reduction in acid solution ordinarily one of the oxygens is reduced to water and the other two liberated as molecular oxygen. The gas is fairly stable toward decomposition into oxygen, and condenses 112.4C, The melting point is to a blue liquid at 249.7. It has a very pungent, characteristic odor, and unlike oxygen it is not magnetic. Ozone is more soluble in water than is oxygen, and is still more soluble in alkaline
34
REFERENCE
[Ch.
lit
solution.
The
solution contains perhydroxyl ion,

3
2 ~.
+ 20H- =
20 2 ~
+H
The latter is
unstable in acid solution.
2HO = H O + O
2
2
2
The potassium
potassium
salt
KO
is
formed by the combustion of
in air.
used in sterilization of water; bleaching of paper pulp, fabrics, and flour; the resinification of oils; and as a deodorant for air in crowded interiors. (Its bactericidal properties in this connection seem not to be very great.) Qualitatively it may be detected by its peculiar odor, by
is
Ozone
its
action
16.
upon potassium
iodide,
and by the blackening
of
silver.
Oxidation-reduction Potentials. Important oxidation reduction potentials involving oxygen and its oxides have been summarized in Table III. Since the first step in the reduction of oxygen is generally the formation of the
peroxide, this potential, equation (2) in determining the action of oxygen.
is
an important factor
reverse
However the
reaction, that is the oxidation of water, does not involve the formation of peroxide as an intermediate step and depends
tentative value is also given for the oxidation of water to free hydroxyl which may be formed as an unstable intermediate under some conditions.
upon equation
(4).
TABLE
III
OXIDATION-REDUCTION POTENTIALS
(1)
(2)
(3) (4) (5)
- O + 2H+ + 2e~ H 30H- - HOr + H + 2<r H - iO + 2H+ + 2e~

2
20H- - i0 2
2 2
2
+H
VOLTS25
2
+ 2e~
2H 2
2
(6)
(7)
- H 2 2 + 2H+ H- 2e~ - Oa + 2H+ + 2er 2 H aO - OH + H+ + e~
+H
0.401 0.68 0.87 1.229

1.77 2.07 2.82
5]
OXYGEN
potentials for the reduction of
35
The
in steps are given in
the following scheme.

Acidic Solution:
2H 2
2.82
nH 1.77
0.72
1.5
0.1
H0
-
Basic Solution:
0.68
2QHj
2.0
n rr
_
0.26
H0 2
||
0.4
0.6
or
0.08
0.87
Chapter IV
GROUP
1.
ALKALI METALS
1. The first group of the periodic system contains the elements stable lithium, sodium, potassium, rubidium, and cesium, and the short-lived radioactive element, francium. They are called the alkali metals because their hydroxides are all soluble bases or alkalies. The most important common characteristics of these elements are the single electron in the outermost energy level of their atoms,, and the comparatively low voltage required to detach this electron from the atom, as shown by the ionizing potentials. Although the outer electron is easily removed, the underlying ones can be removed only by very high potentials; hence ordinary chemical reactions involve the loss or transfer of only a single electron per atom, as illustrated by the = + e~~. equation: Accordingly these elements dis-
M +
1 in their complay invariably an oxidation state of pounds. 2. Atomic and Physical Properties. Many of the physical and chemical properties of these elements may be correlated with the structures of their atoms. (Cf. Table I, also Prin. of Chem., Chap. XVI.) Thus in the solid state the electrons are held so loosely that they can readily pass from association with one atom to another under the impulse of an electric potential hence these elements show in a high degree the conductivity and other properties characteristic of metals. Moreover, since there are not enough outer electrons to serve to bind an atom firmly to all of its
;
36
2]
GROUP
I.
ALKALI METALS
37
neighbors in the solid state,
we
find these metals to be soft,
and
easily fusible.
TABLE
ATOMIC AND PHYSICAL PROPERTIES
Another phenomenon connected with the easy

electrons
loss of
their solubility in liquid amby monia to give highly conducting solutions. The process of solution is accompanied by an ionization of the metal atom
these metals
is
whose electron attaches

thus,
alkali
color,
itself
to a molecule of
3)
ammonia;
(solid)
all
is
= M+
+ e~ (in NH
The
(ammoniated).
The
metals
which
give solutions in ammonia of the same blue due to the solvated electron, the metal ion
all
being colorless in
cases.
addition of
MCI
increases
38
REFERENCE
BOOK OF 'INORGANIC CHEMISTRY
[Ch.
IV
+ and diminishes the blue color in the concentration of accordance with the mass law. The alkaline earth metals
are soluble in liquid ammonia in this way to a smaller extent, and the nobler metals, which hold their electrons more firmly, do not dissolve at all irx liquid ammonia.
The metal vapors are somewhat associated into diatomic molecules at the boiling points of the liquids. The heats of dissociation of the Na 2 and 2 molecules are 18,000 and
12,000 caL respectively. The nuclei of potassium, 40, and rubidium, 87, are not altogether stable, as shown by their slight radio-activity
(cf.
XIII
4).
Spectra* Spectra of the alkali metals are easily excited even the comparatively low temperature of a Bunsen flame suffices to disturb the outer, valence electron; more3.
;
over, since the single valence electron alone is disturbed, unless a high voltage spark is used, their spectra are compara6 length (in mm. X 10~ ) of the prominent lines in the flame spectra are as follows: lithium, 670 red, 620 orange, fainter; sodium, 590 yellow; potassium, 768 red, 404 violet; rubidium, 780 red, 420 blue, 358 violet;
tively simple.
The wave
cesium, 457 blue, 388 violet.

4.
Chemical Properties.
Since the metals
all
give
up
their outer electrons so easily to other substances they are chemically very reactive. Thus, they all decompose water
vigorously, the water taking up the electrons hydroxide ion and hydrogen gas: (solid)
and giving
2 2
+ H O = ^H
OH~. With potassium, rubidium, and cesium the amount of heat developed is so great that the metal takes fire almost instantly when thrown upon water. 6. The ease with which an electron is removed from the
metal increases regularly in going from lithium to cesium, as shown by the ionizing potentials hence we would expect that the ease with which the metal forms any one of its compounds would increase from lithium to cesium; and, conversely, the difficulty of reducing the metal from its
;
+ M+ +
5]
GROUP
I.
ALKALI METALS
39
compounds would be
lithium.
greatest for cesium
and
least for
in general the case, although the simple is somewhat modified by the different sizes and prediction attractions of the resulting ions. The ionizing potentials
is
This
refer to the reaction:
M(gas) =
M + (gas) + e~(gas),
while
the reaction between solid metal and water, previously given, involves in addition the hydration of the M+. This
of energy, and just as the smallest an electron most strongly, so also it attracts water molecules most strongly, a fact which helps lithium metal to react with water to give it a high electrode potential in water solution, as shown in Table I, instead of the lowest as one would conclude from the ionizing potensets free a large
ion, lithium, attracts
tials alone.
amount
This point may be clarified by the aid of the following scheme representing the formation of MCI by a series of steps, which give out or absorb energy, as the case may be.
(solid)
^ M (gas) -> M+ (gas)

+ +
+
p->
C1 2 (gas) -> Cl (gas) -> Cl~ (gas)
MCI
f
(gas)
-*
MCI
(solid)
We have marked each step + in which the system would absorb heat, and each in which the system would lose If potassium were substituted for lithium, steps c heat. and d would naturally remain the same; step a would become smaller (Table I) showing that potassium is more easily fused and vaporized; step b would have a smaller positive value (see Ionizing Potentials) but step e would
;
have a smaller negative value, the last two effects thus tending to offset each other. Although the' heats evolved in formation per mole follow for most compounds the order expected from the ionizing potentials, and illustrated by the iodides, bromides, and chlorides in Table II, the fluorides show the reverse order on account of the small size of the
also
40
REFERENCE
[Ch.
IV
lithium and fluoride ions, allowing close approach and a large negative value for step e.
TABLE
II
HEATS EVOLVED IN FORMATION OF ALKALI HALIDES, KILOGRAM CALORIES PER MOLE
For the same reason, the compounds with other small atoms usually show the greatest stability with lithium rather than with cesium. Other examples include the hydrides, carbides, nitrides, and oxides. The smaller size and larger ionizing potential of lithium
tends to ally
particularly
somewhat with the elements of Group II, magnesium. This is in harmony with the corit
responding resemblance between beryllium and aluminum, boron, and silicon. This resemblance is illustrated by the low solubility of its carbonate and phosphate, as well as by the stability of the compounds mentioned in the preceding
paragraph. 6. The complete transfer of electrons by the alkali metals in the formation of their compounds is illustrated again by the crystal structure of their halides. All except those of cesium crystallize in a cubic lattice of the sodium chloride
type (Append. V;
cf.
also
CsCl type)
in
which the sodium
alternate, and each atom of one kind is surrounded by six atoms of the other, all equidistant from it. It is not possible to designate any sodium atom as belonging tp any particular chlorine atom. There are, therefore, no molecules of NaCl present in the crystal. Now if each sodium atom retained its original electron it would be bound (by an electron pair) to a particular chlorine atom; the absence of such binding shown by the symmetry of the
and chlorine atoms
7]
GROUP
I.
ALKALI METALS
41
crystal lattice is evidence that the electrons have passed over to the chlorine atoms, giving each an extra electron,
and leaving the sodium atom as sodium ion, Na+. Indeed, we have only to melt the crystal, releasing these ions from their fixed positions, and the substance becomes an excellent electric conductor, quite unlike a substance such as sulfur, which is an insulator in
making
it
chloride ion, Cl~,
the liquid as well as the solid form. The solution of an alkali halide in water merely substitutes the attraction of its ions for water for their attraction for each other. The energy of
hydration
is
very high (Table
I)
and serves to overcome the
large electrostatic force responsible for the cohesion of the

crystal. The fact that lithium has the largest energy of hydration is noteworthy in connection with the high solubility of many
of its salts.
is
The salts of low solubility are those where there an especially high attraction between the lithium ion and
the negative ion in the crystal, as in the case of the fluoride. 7. Occurrence. From the average composition of igne-
ous rocks, the percentage of the alkali metals present is estimated as, sodium 2.85, potassium 2.60, lithium 4 X 10~ 6 and rubidium 10~6 and cesium 10~7 Spectral lines of lithium
, .
spectra of the other alkalies are not found in the chromosphere of the sun
in the sun.
and sodium are prominent
The
doubtless because the temperature is sufficient to remove Potassium and rubidium the outer electron completely.
can, however, be observed in the cooler portions. Sea water contains about 2.8 per cent of sodium chloride and 0.08 per cent of potassium chloride, and the evaporation of inland seas has resulted in enormous deposits of these
These deposits of chlorides, and also deposits of carbonates, sulfates, and nitrates are discussed under the corresponding salts. Most plants contain from 4 to 6 times as much combined potassium as sodium, a fact responsible for the use of potassium compounds as one of the important
salts.
fertilizers.
The
ashes of sea weeds, however, contain
more
42
REFERENCE

TABLE
III
[Ch.
IV
SUMMARY OF THE MORE IMPORTANT REACTIONS OF THE ALKALI METALS 4M 4- O 2 = 2M 2O Li, Na at low temperature Li slightly, Rb and Cs 2M -f O 2 - M 2O 2
M
6M 2M 2M 3M 2M 2M 2M 3M 6M 2M
-f
+ + + + + +
-f
+
-j-
5M +
= MO 2 N 2 = 2M N X 2 = 2MX S = M 2S P = M P = 2M + -f 20H- -f H 2H 2C H OH = 2C 2 H 6OM + H 2 2NH (gas) = 2NH M + H AlClj = 3MC1 -f- Al B 2O = 3M 2O -f- 2B H 2 = 2MH MN0 = 3M 2O + iN 2
2
8
spontaneously in dry air K, Rb, Cs, Na at high pressure Li only
With halogens With Te also With As, Sb also
At high temperature At high temperature
sodium than potassium carbonate, with certain exceptions. The alkalies are found in varying amounts in nearly all The three commercially important lithium minsilicates.
erals are: amblygonite,
LiAlFPO 4 spodumene, LiAl(SiO 3 )2;

;
lepidolite, Li 2 [F, OH] 2 Al 2 (SiO 3 )2. The principal source Potasof cesium is the mineral pollucite, 2 Cs4Al4(SiO 3 )9. sium feldspar, KAlSi 3 Os, is a constituent of granite.
and
Preparation and Uses of the Metals. Lavoisier, in 1793, predicted that the "alkalies" would prove tp be
8.
Humphry Davy isolated sodium and by electrolysis of their hydroxides. This potassium method was long employed in the technical preparation of sodium. The metals may also be prepared by the reduction
metallic oxides.
Sir
in 1807
of the hydroxide or carbonate at moderately high tempera-
The
with iron, calcium, carbon, or other reducing agents. reduction by less electropositive elements is accomplished through the greater volatility of the alkali metals. The reduction with calcium furnishes probably the simplest
tures,
laboratory method of preparing rubidium and cesium. Until recently sodium has been prepared commercially by the electrolysis of the fused hydroxide. Now in America most of the metal is prepared by the Downs process which
10]
GROUP
I.
ALKALI METALS
43
employs the fused chloride. The normal melting point of the sodium chloride is lowered to about 600 C. by the addition of sodium carbonate. The sodium is liberated at
the cathode, rises to the surface of the electrolyte as a liquid and is drawn off. Chlorine is liberated at the anode. Potassium is more difficult to prepare because of its greater solubility in the electrolyte. Some is made by the displace-
ment of potassium from its carbonate by sodium vapor. About 20,000 tons of sodium produced yearly in America
are converted to a lead alloy for use in the synthesis of lead Other uses are the manufacture of sodium tetraethyl.
peroxide and cyanide, and in the preparation of organic chemicals where a powerful reducing agent is required. The
manufacture of photoelectric cells consumes some cesium but the amount required per cell is small. During the war potassium was burned to form KO 2 for use in oxygen rebreathers or masks, 2KO 2 + CO 2 = K 2 CO 3 + 1O 2 Sodium amalgamates with mercury with al9. Alloys. most explosive violence. The amalgam is often used in place of the solid metal as a reducing agent. An alloy of 24 per cent sodium and 76 per cent potassium is liquid down 12.6. This is sometimes used to remove traces of to water from gases. Lithium is more like the elements of the second and third groups (Par. 26) and therefore alloys with them more readily than do sodium or potassium. Its alloy with aluminum may achieve commercial importance on account of its very low density. A lithium lead alloy is used for cable sheath, and small amounts of lithium are sometimes added to copper alloys as a "deoxidizer." are formed IjD. Hydrides. Compounds of the type
.
MH
hydrogen upon the heated metals. appearance and are of interest because of their analogy to the alkali halides. The electrolysis of the molten hydride results in the liberation
by the
direct action of
These compounds are
salt-like in
of
possesses a negative charge.
hydrogen at the anode, indicating that the hydrogen Sodium hydride is employed
44
REFERENCE
[Ch.
IV
commercially as an agent for descaling iron and other
oxygen upon lithium the monoxide, Li 2 O, and a trace of lithium perproduces oxide, Li 2 O 2 with sodium the peroxide, Na 2 O 2 is produced;
direct action of
; ,
metals: Fe 3O 4 11. Oxides.
+ 4NaH =
The
3Fe
4NaOH.
and with potassium, rubidium, and cesium the oxide, MO? The monoxides cannot be prepared by dehydraresults. tion of the hydroxides, but may be formed by the action of the metal upon the nitrate, e.g. 5K + KNO 3 = 3K 2 O
oxides of the type, M2O 2 are salts of hydro2 are derivatives of the gen peroxide, while the type Ill The only oxide unstable compound 2 (cf. 14).
2.
,
+ JN
The
MO
HO
of commercial importance is Na 2 2 which is used extensively as a source of oxygen and hydrogen peroxide under
name of "oxone." The peroxide hydrolyzes in water with the formation of H 2 O 2 When a small amount of water is used upon an excess of sodium peroxide, the liberated hydrogen peroxide decomposes with evolution of oxygen.
the
.
is made commercially by heating sodium in from carbon dioxide to a temperature somewhat dry above 300. The principle of counter currents is employed. 12. Hydroxides. The older methods of manufacture used the reaction between a dilute solution of the alkali 2Na+ + CO 3 carbonate and milk of lime. + Ca ++ = CaCO 3 + 2Na+ + 2OR-. Half of the hydrox+ 2OH~
Sodium peroxide
air free
country is produced by this process. manufactured by the electrolysis of a solution of the alkali chloride, a process which results in the formation of the hydroxide and hydrogen at the cathode and chlorine at the anode. The cell reaction is: 2H 2 O + 2C1- 2OH~ + H 2 + C1 2 In carrying out this elec-
ide
consumed
in this
The balance
is
trolysis the cell must be constructed so as to prevent the interaction of the hydroxide and the chlorine, which would give hypochlorite at low temperatures or chlorate at higher
temperatures. This problem is not altogether easy since* the hydroxide moves toward the anode under the electric
12J
GROUP
I.
ALKALI METALS
and the chlorine is somewhat soluble in the brine. cell used most extensively in the United States, has a carbon anode and perforated steel cathode. The brine percolates through the cell and out of the perforations
field
The Nelson
is swept back and prevented from reaching the anode. The liquid coming from the cell contains a mixture of the hydroxide and chloride. Upon evaporation the greater portion of the
in the cathode at such a rate that the hydroxide
chloride
is
precipitated.
process takes advantage of the fact that sodium or potassium may be electrolyzed from a concentrated brine solution with a mercury cathode to form a dilute amalgam, and this amalgam will react with water to form a dilute hydroxide solution. The cell employed is in-
The Castner-Kellner
TABLE
IV
PRODUCTION AND CONSUMPTION OF SODIUM COMPOUNDS IN UNITED STATES IN 1948
46
REFERENCE
[Ch.
IV
reactions.
geniously constructed for the continuous operation of these The process gives a very pure product. Commercial sodium and potassium hydroxides may con-
tain, in addition to large
amounts
of chloride,
bonate, sulfate, nitrate, phosphate, acetate, as well as small amounts of the other alkalies. The hydroxide, sold as "pure by alcohol," has been dissolved in alcohol
some carand peroxide,
which separates out most of the impurities, but leaves a A hydroxide free chloride, carbonate, and acetate. from the negative impurities may be made by treating a solution of purified alkali carbonate with silver carbonate and boiling the resulting solution with carefully purified
little
lime in a silver dish.
sodium hydroxide in the more important industries is given in Table IV. Potassium hydroxide is used less extensively than the sodium compound
of
Its principal use is in the manuits greater cost. of soft soap, which owes its properties to the facturing greater solubility of the potassium compound. 13. Sodium Carbonates and Bicarbonates. Sodium car-
The consumption
because of
bonate
is
found in high concentration in the lakes of
many
arid regions. Mono Lake and Owen's Lake in California contain millions of tons capable of rather cheap extraction.
were formerly the combut it is now manufactured from salt, sodium chloride. The Le Blanc process was the earliest (1791) method employed on a large scale for the conversion of chloride to carbonate, but the method is rapidly becomof certain sea plants
The ashes
mon
source of the
ing obsolete.
(1)
(2)
The
steps in the process are

2
(3)
(4)
+ H SO = NaHS0 + HC1 NaHSO + NaCl = Na SO + HC1 Na SO + 2C = Na S + 2CO NajS + CaCO^ Na^COsjtâfiL

NaCl
2 4
occurs readily upon gentle heating, but reaction (2) requires a much higher temperature. The third
(1)
Reaction
13]
GROUP
I.
ALKALI METALS
47
in a rotary furnace at a temperature of 700-1,000, the charge consisting of a mixture of the sodium sulfate with coal dust and limestone. The product, called " black ash," is extracted with water and impure carbonate, Na 2 CO 3 'H 2 O, obtained by crystallization.
and fourth steps are carried out
The
sulfide residue is usually oxidized to free sulfur
and thus made a profitable by-product.
The Solvay or ammonia process has now largely superseded the Le Blanc. It is based upon the reactions
:
(1)
(2)
Na++Cl-+NH3+H 0+CO2 = NaHCO3+NH4 + +Cl2NaHC0 = Na C0 +H O+CO

2 3 2
Reaction (1) depends upon the slight solubility of sodium bicarbonate in the solution at a temperature of 15 C. or below. The reaction is carried out by first saturating the
brine with
lowing
this the solution is cooled
ammonia, and then with carbon dioxide. Foland the bicarbonate re-
moved by filtration. Reaction (2) takes place
upon
70
gentle ignition. The success of the process depends upon the re-
covery of the ammonia by the reaction: 2NH 4 C1
50
fit
+ Ca(OH) = 2NH 3 + CaCl + 2H O. Lime2

2
2
30
stone serves as the source

10
of both the carbon dioxide
and
the
lime:
2.
CaCO =
-10
CaO + CO
10
20
Per cent Na 2 C0 3
30
40
The phase relations of the

various hydrates are indicated in Fig. 1. The anFIG.
1.
The system sodium carbonate

and water.
hydrous salt is known commercially as soda-ash and the decahydrate as washing soda. As the salt of a weak acid, sodium carbonate is hydrolyzed in solution, IN Na 2 COg
48
REFERENCE
[Ch.
IV
containing about 0.01N OH""; and many of its uses, such as washing, depend upon this property. As a salt of a weak acid, it is also used to neutralize strong acids and in the preparation of their sodium salts. The consumption of sodium carbonate by various industries is given in Table IV. Sodium bicarbonate, the common household baking soda, is obtained as a step in the Solvay process. With the excep1200
tion of lithium, the alkali bicarbonates are all more insoluble than the carbonates.
1000
800 600
The conversion
to
of
bicarbonate
difficult
carbonate
the
by heating becomes more

the
higher
atomic weight of the

200
alkali,
as
J
indicated in the plot of decomposition pressures

is
80
FIG.
2.
100
120"
140
160
180
(Fig.
2).
Advantage may
Temperature
be taken of the reversible
Decomposition pressures of
alkali bicarbonates.
reaction,
2
COg" + CO
3 ~,
+ H O = 2HCO
to con-
vert carbonates into bicarbonates. When a bicarbonate solution is evaporated at 100 or above, sodium sesquicar-
bonate, Na 3 (CO 3 ) (HCO 3 )-2H 2 O separates. The bicarbonate is employed in baking, the use depending upon the liberation of carbon dioxide with acid, as does also its use in certain types of fire extinguishers. The ease of purification of sodium bicarbonate by crystallization renders it a valuable standard in the titration of acids and bases. For this use it is fused to convert to the carbonate and to remove the last traces of water. This operation should be carried out in an atmosphere of CO 2 since the decomposi,
tion pressure of
Na CO
2
is
2.2
mm.
at 700
and
6.2
mm.
at
1,000.
14. Potassium Carbonates. For centuries potassium carbonate was extracted from wood ashes; hence its name,
16]
GROUP
I.
ALKALI METALS
the chloride
49
potash. It
ate
is
may
be
made from
by the Le Blanc
is
process, but not
by the Solvay
process, since the bicarbon-
not sufficiently insoluble. However the conversion
generally carried out: (1)
by the
precipitation of
KHCOa
under pressure into a susof MgCO 3 in KC1 solution and (2) the recovery pension of the potassium carbonate from the double salt by decomposition with hot water giving insoluble MgCO 3 and a solution of potassium carbonate, 2MgKH(CO 3 )24H 2O = 2MgCO 3 + K 2 CO 3 + CO 2 + 9H 2 O. Other sources are the mother liquors obtained in the manufacture of beet sugar, wine-lees, and water used in washing crude wool which contains potassium fatty acids. In each case the
3
2
MgCO
*4H 2 O by passing
CO
organic material is ignited to give the carbonate. Potassium carbonate crystallizes as the dihydrate.
It is
used in making soap and hard

industries.
glass,
and
in the textile
Potassium bicarbonate is similar in chemical properties to the sodium salt but is about three times as soluble. 15. Lithium, Rubidium, and Cesium Carbonates. Lithium carbonate is the most important commercial compound of that element, is used in medicine, in the preparation of
glazes,
other lithium compounds, in ceramics for producing high and in the glass industry for making special glasses
with high fluidity when molten. Its solubility is sufficiently low so that it may be prepared by precipitation from a solution containing lithium ion
by the addition
is
of
sodium
car-
bonate. Lithium bicarbonate
soluble.
The rubidium and cesium carbonates and bicarbonates

resemble the potassium compounds.
16. Fluorides. The alkali fluorides do not occur free in nature to any large extent, although sodium aluminum fluoride, Na 3 AlF6 cryolite, occurs in large deposits. The fluorides are usually prepared by the action of hydrofluoric acid upon the carbonate. With excess of the acid they tend or even MHsF4 to form acid fluorides such as 2
,
MHF
50
Ktl-tKtINLt
bOVJK
IIN^JKtJ/MNIV.
n.
IV
These acid compounds are sometimes used as a method of preparing pure hydrogen fluoride, since they readily decompose with the evolution of the gas. Lithium fluoride is but slightly soluble. Sodium fluoride has some use as an insecticide and a wood preservative. It is also
(cf.
10).
used in the preparation of complex fluorides. Alkali chlorides are found in great de17. Chlorides. from the evaporation of inland lakes or posits resulting
seas.
Sodium
chloride.
In
many
places great beds of almost
pure sodium chloride have been located and from these salt is taken by ordinary mining operations. In regions removed from naturally occurring salt deposits, sodium chloride is obtained from sea water or salt wells usually by solar evaporation in shallow ponds. Crude salt generally contains traces of calcium and magnesium chlorides which are objectionable because of their deliquescence. Pure sodium chloride may be precipitated from a concentrated brine
of hydrogen chloride gas, due, in part, to the in concentration of chloride ion. The reaction qualincrease
upon addition
itatively
is
that predicted
by the Mass Law. The solubility of sodium

chloride changes but slightly
with temperature, being 26.3 per cent at and 28.1

per cent at 100. Phase relations in the salt-water sysare given in Fig. 3. The crystal structure has been
tem
20
Per cent NaCI
30
40
discussed in Paragraph
6.
The production of salt in the United States in 1938 was about nine million tons. Of this three million tons were used in the preparation of the carbonate by the Solvay process. Other important industrial uses include refrigeraFIG.
3.
The system sodium

and water.
chloride
19]
GROUP
I.
ALKALI METALS
51
tion; agriculture; household; metallurgy of silver, copper,
and lead; tanning; preservative; ceramics; salting out of soap; preparation of hydrochloric acid and sodium sulfate by reaction with sulfuric acid; and the preparation of sodium hydroxide and chlorine by electrolysis. 18. Potassium Chloride. For many years Germany enan almost complete monopoly of potassium salts joyed
through the possession of the extensive deposits of chloride at Stassfurt in Prussia. Since 1930 there has occurred a rapid development of the potash deposits in the United States. These have been principally the deep lying saline
deposits in
Mexico and the natural brines of Searles Lake in California. Over a million tons of potassium salts, chiefly chloride, were produced from these sources in 1948. The major portion of the potassium chloride of the Stassfurt deposits is in the form of double salts of magnesium and calcium chloride, sulfate, and borate. The most important of these is carnallite, MgCl 2 *KCl'6H 2 O, and to a lesser extent kainite, MgSO 4 -KCl-3H 2 O. Potassium chloride is extracted by dissolving carnallite in hot magnesium
chloride solution; cooling this solution precipitates the greater part of the potassium chloride. The production of
New
potassium chloride at Stassfurt in 1938 was in excess of 1,500,000 tons. The dust from blast furnaces manufacturing pig iron, and the dust from cement kilns, has been
shown to contain potassium chloride and also sulfate in recoverable amounts. It is estimated that the United States could produce several hundred thousands of tons yearly from this source. The most important uses of the potassium chloride are as fertilizer (about 90 per cent) and in the production of potassium hydroxide and other potassium compounds. Growing tests indicate that the production of grain in this country could be increased 30 per cent by the average use of 50 Ibs of 2 O per acre.
Lithium, Rubidium, and Cesium Chlorides. Lithium It forms mono-, chloride is the most soluble of the group.
19.
52
REFERENCE
[Ch.
IV
and tri-hydrates, and in many respects resembles magnesium chloride. One of the most important sources of rubidium and cesium chlorides is the mother liquor remaining after the extraction of the potassium chloride from carnallite. These elements are usually separated from the liquid by conversion into the relatively insoluble alums through the addidi-,
aluminum sulfate. Bromides and iodides occur 20. Bromides and Iodides. in sea water and in the various salt deposits. They are not
tion of
recovered as such, but the halogens are liberated as the free elements, and the salts prepared from the elements by methods discussed under the halogens. Sodium and potas-
sium bromides are used
in medicine as sedatives, and in for precipitating silver bromide and as rephotography The alkali iodides find limited tardants in developers.
application in photography, and in medicine to supply iodine to the thyroid gland, and sometimes in tincture of
iodine, to increase the
amount
of iodine that
can be
dis-
solved.
21. Cyanides. Sodium cyanide is made on a large scale from sodium amide (Table III) by reduction with carbon at red heat: NaNH 2 + C = NaCN + H 2 A mixture of sodium and potassium cyanides may be prepared by the reduction of potassium ferrocyanide with sodium: K4 Fe(CN)6 + 2Na = 4KCN + 2NaCN + Fe. Potassium cyanide is also manufactured by the action of ammonia upon a mixture of potassium carbonate and carbon at a high tempera.
ture:
K CO + 2NH + 4C
2
= 2KCN + 3CO + 3H
2.
The
very soluble in water, and the solution is alkaline due to the hydrolysis of the cyanide. The quite uses of these compounds in gold mining and electroplating
alkali cyanides are
depend upon the formation of complex cyanides with gold, silver, and platinum. The sodium salt is now generally used due to the fact that it is cheaper and gives a higher weight
of cyanide per
pound
of salt.
Like
all
substances giving
23]
GROUP
I.
ALKALI METALS
53
cyanide ion or hydrogen cyanide in solution, these salts are very poisonous. The alkali sulfates and double sulfates 22. Sulfates. with calcium and magnesium are found in the various salt
lakes
and
salt deposits.
sium, as
KNaSO
4,
Double sulfate of sodium and potasand various types of sodium and potasin volcanic lava.
sium alums are of frequent occurrence
sulfate, called salt cake, is a product of the manufacture of hydrochloric acid from sodium chloride. Some potassium sulfate is extracted from the Stassfurt deposits. Sodium sulfate is used in medicine as a cathartic and in
Sodium
the manufacture of cheap glass to furnish the sodium. Its principal use (over 400,000 tons annually) is in the
"sulfate" process for the manufacture of wood pulp. It can be crystallized as Na 2 SO 4 '10H 2 O, Glauber's salt, below 32.384, and as the anhydrous sulfate above that tempera" ture. The transition point serves as a convenient fixed in the standardization of thermometers. The solupoint" bility of the decahydrate increases rapidly with temperature and the solutions formed at the higher temperatures may be readily cooled in the supersaturated state. If a particle of this solid hydrate is then added, crystallization takes place and the whole solution appears to solidify. An unstable heptahydrate may be crystallized out below 24 C. Potassium sulfate is used in the preparation of potassium alum and also as fertilizer, being preferred to the chloride for this purpose with certain crops, especially tobacco. 23. Nitrates. Alkali nitrates are formed in nature
through the decomposition of organic material. Due to the solubility of these salts, deposits are found only in the rainless regions of the earth. By far the most important occurs in Chile, and is composed chiefly of sodium nitrate. Com" mercial Chile saltpetre," consisting of 95 to 98 per cent sodium nitrate, is made by extracting the crude nitre rock with water. Chile saltpetre was formerly almost the only source of the nitric acid and nitrate-fertilizer, but now has
54
REFERENCE
[Ch.
IV
been largely replaced by the various processes for the fixation of atmospheric nitrogen (cf. XII 32). The uses of the alkali nitrates which depend upon the oxidizing power of nitrate are discussed under the chemistry of nitrogen. Potassium nitrate absorbs water less readily than sodium nitrate, and for this reason was formerly used more extensively than the sodium salt in gunpowder. Potassium nitrate is prepared from the sodium by double decomposition with potassium chloride, taking advantage of
the fact that the solubilities of potassium chloride, potas-
and sodium nitrate increase rapidly with temwhile that of sodium chloride is hardly affected. perature, The sodium nitrate is dissolved in hot water and concensium
nitrate,
most of the sodium

ing, followed
trated potassium chloride solution is added, whereupon is precipitated as chloride. The solumore sodium chloride first separattion is then evaporated,
by potassium
nitrate.
crystal structure of sodium nitrate is similar to th simple cubic arrangement of sodium chloride (Par. 6), the nitrate group as a whole occupying the positions corre-
The
sponding to the chloride
ion.
The
alkali nitrates differ
from
the nitrates of most of the other metals in that upon heating they first decompose into nitrite and oxygen. Upon further
heating nitrogen and oxygen are evolved and the oxide and peroxide formed. A mixture of 45 per cent sodium and 55 per cent potassium nitrates melts at 220 and is a convenient high temperature liquid bath. 24. Other Salts of the Alkali Metals.
alkali metals
rate,
Compounds
of the
with
sulfide,
thiosulfate, chlorate,
perchlo-
phosphate, borate, and silicate are of importance, but since their ^properties and uses depend so largely upon the chemistry of negative ions, they are discussed in the chapters dealing with those ions. 26. Chemical and Analytical Properties of Ions. The characteristic of the alkali ions is the slight outstanding tendency to form insoluble salts or complex ions. As already
25]
GROUP
I.
ALKALI METALS
55
mentioned, lithium resembles the alkaline earth metals in

lithium fluoride, carbonate, and phosare moderately insoluble and the bicarbonate more phate soluble than the carbonate, like the alkaline earth metals, and unlike the rest of the alkalies. Lithium ion is slightly
many respects. Thus
hydrolyzed. The chloroplatinates, acid tartrates, and alums of lithium and sodium are soluble, while the corresponding
salts of potassium, rubidium, and Potassium forms with soluble.
cesium are relatively
in-
sodium
cobaltinitrite in
It is the least
dilute acid the precipitate,
K NaCo(NO
2
2 )e.
soluble of the potassium compounds, but this does not serve to distinguish potassium from rubidium, cesium, or am-
monium, which form corresponding compounds. Potassium picrate, C 6 H 2 (NO 2 )3OK, potassium perchlorate, KC1O 4 and sodium and potassium fluosilicates, Na 2 SiF 6 K 2 SiF6 are also but slightly soluble. Sodium antimonate, NaSb(OH) 6 is the least soluble of the sodium salts. Sodium may be precipitated from solutions containing potassium by use of the
,
uranyl zinc acetate reagent. The formula of the precipitate is NaZn(UO 2 ) 3 Ac9*6H 2 O. For quantitative determinations the conditions for the precipitation must be carefully controlled.
Potassium ion appears to be more readily adsorbed than sodium ion, and this in part accounts for the much smaller quantity of potassium salts in sea water, although another factor may be its more ready precipitation as an iron silicate,
KFeSi 2 O6
In the quantitative analysis of the alkalies, they are usually converted tb the chlorides and the mixture weighed. The lithium chloride may be extracted by dissolving in amyl alcohol. Potassium, rubidium, and cesium are converted to the chloroplatinates, and the sodium obtained by
Although rubidium and cesium are rarely present they may be separated from potassium by taking advantage of difference in solubility of the acid tartrates.
difference.
in quantity
In addition to the use of the spectroscope in the identifica-
56
REFERENCE. BOOK
OF INORGANIC CHEMISTRY
[Ch.
IV
tion of the alkalies, advantage is taken of the color imparted to the Bunsen flame by the presence of volatile compounds
of these elements.
Lithium colors the flame
red,
sodium
yellow, potassium violet, rubidium bluish red, and cesium blue. The sodium flame test is of extraordinary delicacy, 10 being capable of detecting 10~ grams of sodium. Since
present in practically every substance, it is necessary in making a flame test for sodium to judge the amount of sodium present largely by the length of time that the intense yellow color persists in comparison to pure sodium chloride as a standard. The potassium flame test is about five thousand times less sensitive than the sodium test. In the presence of any considerable amount of sodium it is necessary to use a thick blue glass to cut out the yellow sodium light in order to detect the potassium. 26. Francium. The first isotope of element 87 to be discovered was a member of the naturally occurring actinium decay series, (cf. XXII). In 1939 M. Perey observed a 227 branching of the decay chain (about 1 per cent) at Ac
this quantity of
is
sodium
which produces Fr 223 by alpha-emission.

this isotope
is
The
half-life of
only 21 minutes.
Since that date four other
radioactive isotopes have been made by nuclear-bombardment reactions. All of these additional isotopes have halflives shorter
than that of Fr 223
,.
Chapter
C3ROUP
1.
II.
ALKALINE EARTH METALS

may
be divided into a main
On
the basis of their atomic structure the elements
with two valence electrons
group consisting of beryllium (formerly often called glucinium from the sweet taste of some of its compounds), magnesium, calcium, strontium, barium, and radium, and a As a common subgroup, zinc, cadmium, and mercury. characteristic the main group elements have kernels with the same number and arrangement of electrons as the preceding noble gas, while the subgroup elements have kernels with eighteen electrons in the outer shell. Beryllium and magnesium are smaller and much less basic than the rest
of the
in
main group, and before the fundamental
differences
classified
atomic structure were recognized, they were frequently with the subgroup elements. The remaining elements of the main group have hydroxides with distinctly alkaline properties and have long been known as the alkaline earth elements, and we shall use the term as applying
to
all 2.
of the
main group.
Physical Properties of Metals.
The elements
in the
free state are highly metallic.
They have grey white luster
when freshly cut, but readily tarnish, especially the heavier members of the group. Although somewhat brittle, they may be hammered and rolled. Beryllium is hard enough to
scratch glass, while barium is but slightly harder than lead. are good electrical conductors the specific conductivity of calcium is about 45 per cent that of silver.
The metals
57
58
REFERENCE

I)
[Ch.
Their melting points (Table

of the alkali metals.
are
much
higher than those
TABLE
ATOMIC AND PHYSICAL PROPERTIES OF ALKALINE EARTH ELEMENTS
3.
Chemical Properties.
are present in the
In
all
of their
compounds the
i.e.
elements
of the
2 oxidation state,
lost
both
two outer electrons are always
when
the elements
It will be observed (Table I) that the oxidation potential of the heavier members of the group is as great as that of the alkali metals. Thus barium readily reacts with water, losing its electrons to the hydrogen
enter into chemical reactions.
and forming barium ion and molecular hydrogen: Ba + 2H 2 O = Ba++ 4- 2OH~ + H 2 The mechanism of the reaction involves taking the two electrons away from the barium and this, as given in Table I, requires about five volts for the first electron and ten for the second. These
of the water
.
values of the ionization potentials are higher for the alkaline earth metals than for the alkali metals, and the reason that
3]
GROUP
is
II.
59
barium
so readily oxidized to form the ion is to be found in the large heat of hydration of the barium ion. However, the rate of reaction of the second group elements with water
slower than that of the alkali metals, even in the case of the more electropositive members; and magnesium and beryllium are scarcely attacked by water alone at
is
much
ordinary temperatures. The metals burn brilliantly when heated in air or oxygen, forming the monoxide, except in the case of barium, which forms the peroxide. A certain amount
of the nitride
is
also
formed when burned
in air, especially
with magnesium, calcium, and radium. Because of their highly electropositive character the metals burn readily when ignited in carbon dioxide, forming the metal oxide and carbon. At low temperatures the metal surfaces are protected from rapid oxidation by oxide films; this is particularly true of beryllium and magnesium. Beryllium does not dissolve with appreciable speed in water even when boiled. Magnesium evolves hydrogen very slowly with cold water, while with calcium a slow stream of bubbles is observed. The metals all dissolve rapidly in acids. Beryllium dissolves in the alkali hydroxides in a manner similar to =
aluminum: Be
+ OH~ + H O
2
HBeO
+H
2.
Due
to
TABLE
II
REACTIONS OF GROUP
II
METALS
Ba
also forms
2M+O = 2MO M 4- 2H O = M(OH) M + H = MH

2 2 2 2
Ba0
+H
2
Very slow with Be and Mg With Ca, Sr, and Ba at

high temperature
4M
M + 2H+
442
M+-<
4-
10H-
NO
2
2 3
+- H
S
= 4M++
+ NH + + 3H O
4
2
With
dilute acid:
also
M
M M
X = MX
2
3
evolved
3M + N = M N 3M 4- 2NH = M N + 3H
3
X =
2
4-j-
= MS 2C = MC 2
2P =
2 any halogen High temperature Heated Also with Se and Te
Especially
with
Ca,
Sr.
1M
4-
i!M 4-
CO 2 = 2MO
P2
4-
High temperature Heated
Buix* i n
CO
60
REFERENCE
[Ch.
their action as strong reducing agents the metals are oxidized by many of the negative elements. A summary of the more important types of reactions is given in Table II. None of the elements of the group exists 4. Occurrence.
The estimated percentages of the elements in rocks are: calcium, 3.63; magnesium, 2.09; barium, igneous 4 5 and 0.05; strontium, 1.9 X 10~ beryllium, 1 X lO" 12 radium, 10~~ Beryllium compounds do not occur in large
free in nature.
; ;
.
deposits but small quantities are found in many minerals and granitic rocks, usually as complex silicates and aluminates.
6SiO 2
The most important mineral is beryl, 3BeOAl 2 O 3 Colored dark green with chromium it is known as
emerald.
shire.
A blue-green form is aquamarine.

A MgCO
3
4
Masses of beryl
in
weighing more than a ton have been found
New Hamp-
The elements
are:
3 )4;
tically all
are found in combination with pracfew of the more important of the acid oxides.
minerals
magnesite,
asbestos,
talc
;
H Mg
2
(SiO
3
;
CaMg
;
(SiO 3 ) 4
or soapstone, 3 dolomite,
MgCO
MgCl -KCl-6H 2 O; CaSO -2H 2 O; fluorspar, CaF 2 limestone, CaCO gypsum, = Cl or F); strontianite, SrCO 3 apatite, Ca (PO 4 ) X, (X barites, BaS0 4 Magnesium and calcium chlorides and sulspinel,
CaCO
Mg(AlO 2 ) 2
3
;
carnallite,
fates are present in sea water, the former in
somewhat
larger
concentrations.
of animal
Both elements are found as
integral parts
and vegetable matter, although calcium is more than magnesium. prevalent Radium is widely distributed in almost all rocks but in extremely small quantities. Primary uranium minerals contain about 3.4 X 10~7 grams of radium per gram of uranium
(cf.
xxm).
Metals: Preparation and Uses. The metals are generally prepared by the electrolysis of their molten chlorides or fluorides to which alkali halides have been added to decrease the melting point. The common commercial electro5.
magnesium is 70 per cent magnesium chloride and 30 per cent sodium chloride. The recently developed carbolyte for
5]
GROUP
II.
61
and silicothermic processes show considerable promise. In the former a mixture of magnesium oxide and coal is heated to 2300 C. in an electric furnace and magnesium vapor distilled off. In the latter the oxide is reduced by ferro-silicon in the presence of lime. 2MgO Si(Fe)
thermic
2CaO = 2Mg
rier of
Ca SiO 4
2
(Fe).
The
iron acts as car-
the silicon and takes no part in the reaction. Calcium is prepared by the electrolysis of a mixture of the chloride and fluoride in a graphite crucible, which acts as the anode.
The cathode is an iron rod just dipping into the molten salts. The liberated calcium adheres to the rod which is
slowly raised, thus forming a long "stalk" of calcium.
Beryllium and magnesium chlorides may be reduced by sodium or potassium at high temperatures and barium oxide As a war emergency, a is reduced by silicon at 1200 C. process was developed for the production of calcium by reduction of calcium oxide by aluminum, the reaction being
at 1200 C. used in signal flares and in photographic Magnesium flash lights, usually in the form of powder; the latter use depends upon the high proportion of ultraviolet light in the flame formed by the combustion of the metal. It is also made into ribbon, the major part of which is now used in the degasification of radio tubes. Its importance in this connection is due to the absorption by the heated metal, not only of oxygen, but also of nitrogen through the formaIt is employed as a deoxidizer in tion of the nitride, Mg 3 N 2
carried out in
is
.
vacuum
casting bronze, nickel-silver, and monel metal. A small per cent of magnesium added to aluminum greatly increases the ease of machining of the latter. The composition of a num-
ber of magnesium alloys which are trade-marked, Dowmetal, A. M. Alloys, and Bohnalite X, is given in Table III. Because of their low density (1.8) and high tensile strength these alloys are now widely used in the construction of airplanes, portable tools, and other machinery where light weight is important. The alloys are frequently treated
62
REFERENCE

TABLE
III
[Ch.
COMPOSITION OF MAGNESIUM ALLOYS
Mg, Mg, Mg, Mg, Mg,
91.8; Al, 2.0; Mn, 0.2; Cd, 2.0; Cu, 4 89.1; Al, 4.0; Zn, 0.4; Si, 0.5; Sn. 6.0 92; Al, 7.0; Zn, 0.75; Mn, 0.2 88.2; Zn, 4.5; Mn, 0.8; Si, 0.5; Sn. 6.0
9; Al, 91
USE Mold Wrought

Sheet
Press forged
Mold
with chromic or selenious acid solutions to give their surfaces a corrosion resistant film. Calcium metal is used as a deoxidizer in the manufacture of many alloys and special steels. It is volatile at the temperature of molten steel and leaves no metallic residue. Some calcium silicide is used instead of the metal in certain steels. Although pure beryllium is brittle and has no industrial application, its alloys are rapidly becoming useful com2.25 per cent beryllium alloy with copper is a modities.
A beryllium-cobalt-copper remarkable spring material. alloy combines high electrical conductivity with great hardness. Nickel with 1.8 per cent beryllium can be heat-treated
to give values of tensile strengths as high as 260,000 pounds per sq. in. The addition of 0.5 per cent beryllium hardens
gold and
is
said to increase the resistance of silver to tarnish.

its
nuclear properties, beryllium may become highly important in the construction of nuclear reactors. Radium amalgam is formed upon the electrolysis of radium chloride solution using a mercury cathode. The
Because of
mercury
may
is
be driven
off
by heating
to leave the radium.
The metal
said to blacken quickly
due to the formation
of the nitride.
COMPOUNDS
Oxides. The monoxides are difficultly fusible (Table and extremely stable, remaining undecomposed at IV)
6.
in order of the
temperatures of 3,000 C. Their heats of hydration increase atomic weights.
6}
GROUP
II.
63
TABLE
IV
II
OXIDES OF GROUP
Beryllium oxide is as hard as corundum but the heavier oxides are soft. Beryllium oxide does not react with water.
not ignited too strongly, reacts very slowly, while the rest of the group react rapidly. With lime the hydration reaction is called "slaking." The reaction starts slowly, but the heat evolved soon raises the temperature to a point where the reaction proceeds rapidly. The heat of slaking is sufficient, under some conditions, to cause the ignition of wood or other combustible material; hence
Magnesium
oxide,
if
the accidental slaking of stored lime often results in destructive fires.
The
solid oxides crystallize in the
sodium chloride type
of ion lattice, with the exception of beryllium oxide, which The oxides are exis similar to zinc oxide (Append. V). tremely poor conductors of heat.
The oxides of all except beryllium are generally prepared by the decomposition of the carbonates. The ease of decomposition decreases with increasing atomic weight, that is with increasing basicity of the metal oxide. The manufacture of lime is carried out in tall chimney-like furnaces known as lime kilns. The process is continuous; limestone is fed into the top, is heated and decomposed by a draft of hot gas, and the lime is removed at the bottom of the kiln.
'64
REFERENCE
reaction
is
[Ch.
The
sible to
carried out at as low a temperature as posprevent the fusion of silicates present in the lime-
stone which would render the lime inactive. In order to keep the temperature low the partial pressure of the carbon dioxide must also be kept low. In Fig. 1 are given the pressures of carbon dioxide in equilibrium with the oxide and carbonate at various temperatures. If calcium carbonate is heated in a retort under atmospheric pressure it requires a temperature of 910 C. to bring about decomposition; however, in the operation of the lime kiln the blast of hot 1200 gases through the furnace
800
keeps the partial pressure of the carbon dioxide at a
low
400
figure
and permits the
reaction to go to completion at temperatures much

700
600
FIG.
900
1100
i3ooTc
below 910. In the case of barium carbonate, the de-
composition temperature is so high that carbon is mixed with the charge further to lower the partial pressure of the carbon dioxide: C + CO 2 = 2CO. Barium oxide is sometimes prepared from the nitrate, since it decomposes at much lower temperatures.
1. Decomposition pressures of calcium and barium carbonates.
Magnesia in the form of bricks is used for lining furnaces and other refractory purposes. Mixed with asbestos it is employed as heat insulation for hot water and steam pipes. Other uses include: the manufacture of Sorel cement (Par. 9) absorbent in the manufacture of dynamite vulcan;
;
ization of rubber; adulterant of paint.
Large quantities of mixed magnesium and calcium oxides are used for some purposes in place of pure magnesia, the mixture being produced by the calcination of dolomite. The production of lime in the United States in 1948 was 6,000,000 tons. This was consumed chiefly (1) in making
7]
GROUP
II.
ALKALINE EARTH MEFALS
65
the hydroxide (vide infra), used in plaster by the building industry, (2) in agriculture for soil treatment, and (3) in the chemical industries. Heated in the oxy-hydrogen flame, lime gives out an intense light, hence its former use in the " "lime light. Calcium oxide is often employed as a dehydrating agent, for example, in the preparation of absolute alcohol and the drying of ammonia gas. A mixture of sodium
hydroxide and calcium oxide, "soda-lime," is often employed to remove both water and carbon dioxide from gases. Lime containing more than 5 per cent magnesium oxide does not slake readily and is called "lean." Barium oxide is the only one of the group which may be converted into the peroxide, BaO 2 upon heating in air, although with the exception of beryllium the peroxides may all be prepared by the action of hydrogen peroxide upon the metal ion. Barium peroxide is mentioned in connection with the preparation of oxygen and hydrogen peroxide. With water it readily forms the hydrate, BaO 2 -8H 2 O. 7. Hydroxides. The formation of the hydroxides from oxides has been discussed above. The alkaline reaction of
,
the hydroxides is limited by their solubilities (Table IV) however, the hydroxides of calcium and the heavier members of the group may be classed as strong bases. Their
;
salts
with strong acids are very slightly hydrolyzed. Barium hydroxide is the only one which is stable enough to be heated to fusion.
is amphoteric (Hildebrand, Prin. a fact which is not surprising in view of the of Chem.y p. 214), very small size of Be++ (cf. Ill 7). The freshly precipitated hydroxide is said to have the formula Be 2 O(OH) 2 and is metastable with respect to the form Be(OH) 2 It dissolves in hydrogen ion to form Be++ but this ion hydrolizes &t
Beryllium hydroxide
low acid to form
2Be++
+HO =
2
Be 2 O++
+ 2H+
66
REFERENCE
is
[Ch.
V
or
The hydroxide
Be2O
soluble in hydroxide ion to form
BeO2
(beryllate or deberyllate).
Some magnesium hydroxide is prepared by the action of steam upon magnesium chloride: MgCl 2 + H 2 O = MgO + 2HC1. The hydroxide is precipitated from a solution of
magnesium
ion
upon the addition
of a strong base.
It be*
longs to the class of sparingly soluble bases which are sol+ = uble in excess of ammonium ion: Mg(OH) 2 4
+ 2NH
Mg++ + 2NH 4 OH.

Because of its low cost of production, calcium hydroxide used commercially in many processes requiring hydroxide ion. A suspension of the solid in its saturated solution (milk of lime) is often employed. Among the more important uses are the preparation of mortar, bleaching powder, ammonia, alkali hydroxide purification of sugar and illuminating gas
is
:
;
removal of hair from hides; softening of water (Par. 11). The most extensive use is that in mortar. This is made by mixing slaked lime, one volume, with sand, three or four volumes, and water to make a thick paste. The mortar gradually hardens due, first, to the evaporation of water
and the cementing action
of the deposited hydroxide, and second, to the absorption of carbon dioxide from the air: CO 2 = CaCO 3 There follows a very 2 O. Ca(OH) 2
+H
slow formation of calcium silicate. The setting is accompanied by a decrease in volume but the presence of the large amount of sand prevents a large total shrinkage and renders the product porous. Strontium hydroxide is made by heating the carbonate in = Sr(OH) 2 + CO 2 This reaction steam: SrCO 3 + 2O takes place at a lower temperature than the reaction: SrCO 3 = SrO + CO 2 due in part to the lowering of the partial pressure of the carbon dioxide by the steam, and in part to the energy of formation of the hydroxide from the oxide. The hydroxide crystallizes as Sr(OH 2 -8H 2 O. Strontium hydroxide is employed in the refinement of sugar to recover sugar from dilute solutions. Both calcium and
8]
GROUP
(I.
67
strontium ions form insoluble precipitates (saccharates) with sugar from hydroxide solutions, and these may be
decomposed by the action of carbon dioxide. The strontium compound is somewhat the less soluble but the
general practice in the sugar industry in the United States is to cool in solution and precipitate the calcium saccharate.
Barium hydroxide crystallizes with eight molecules of water. Its solution is known as "baryta- water," and is often employed as a standard alkali in quantitative analysis.
The
barium carbonate keeps the solution free from carbonate ion, which is usually present in sodium hydroxide and which is objectionable in titrating acids when
insolubility of the
certain indicators are used.
Carbonates.^-Normal beryllium carbonate does not exist, but a basic carbonate is precipitated upon the addition of sodium carbonate to a soluble beryllium salt. The precipitate is gphible in excess of the reagent due to the formation of the beryllate ion, Be 2 O3
8.
Normal magnesium carbonate, MgCO 3 occurs in nature as the mineral, magnesite. basic carbonate, 4 (OH) 2 (CO3)*3H 2O, is precipitated when an alkali carbonate is added to magnesium ion. The precipitate is soluble in ex+ + OH"" cess ammonium ion due to the
,
Mg
4
equilibria:
NH
= NH OH,
4
and
NH + +
4
CO.--
+ H O = HCOr
2
JThe carbonate is also soluble (see Calcium Carbonate below). The precipitated basic salt is used in medicine under the name "magnesia alba," partly as a mild alkali and partly for the physiological action of magnesium ion. Considerable quantities are consumed in and of silver polish. The tl^ preparation of tooth powder natural carbonate and also the double carbonate with calcium, dolofnite, CaCO 3 -MgCO 3 are used for the commercial production of carbon dioxide. The compound MgCO 3 (NH 4 ) 2 CO 3 4H 2O is precipitated upon the addition of ammonium carbonate to magnesium ion in a solution con4
,
+ NH OH.
in carbonic acid
68
REFERENCE

Advantage
is
fCh.
taining 30 per cent alcohol.

in qualitative analysis.
taken of this fact
Calcium carbonate crystallizes in two forms, calcite f rhombohedral, and aragonite, rhombic. The latter is unstable in respect to the former but the rate of transition is slow at ordinary temperatures. The heat of transition is about 300 cal. per mole. The carbonate is the most abundant of the calcium compounds. The most common forms are: Iceland spar, which is almost pure calcite; marble;
and contains clay and other silicates; chalk, which has been formed from the shells of minute marine organisms; shells and pearls. The crystal structure of calcite is similar to that of sodium
limestone, which
is less
crystalline
chloride, with the carbonate
group replacing the chloride. The three oxygens are symmetrical aboift the carbon. Because of the size of the carbonate group the unit cube is distorted into a rhombohedron. Calcite is luipinescent under the action of cathode rays. The glow pergfctfi for some time after the action of the rays has been stopped. i Calcium carbonate is precipitated upon the addition of
carbonate ion.
If
the solution
is
boiling the precipitate is
largely aragonite; in the cold it is finely dividecâglcite,
which becomes coarse and distinctly *fystalline Drained upon standing. The solifbility of calcium carbonate is increased in the presence of hydrogerj ion due to the equilib= HCO 3 - (cf. XIII 10? and hence, rium, H+ + CO 8 CaC0 3 + H+ = Ca++*+ HCOr. With excess Icid, carbon
Due to the fact that the is, of course, liberated. second ionization step of carbonic acid is much less than the first, calcium carbonate dissolves in carbonic acid: CaCO 3 + 2 CO 3 = Ca++ + 2HCOr. This reaction occurs wherever water comes in contact with rock or soil condioxide
taining cjalcium (or magnesium) carbonate! and imparts "hardness" to the water, which is objectionable for certain purposes (Par. 10). The bicarbonate solution upon heating loses carbon dioxide and the carbonate is again precipitated*
9]
GROUP
II.
69
and stalagmites are formed in caves by the preof calcium carbonate brought about by the loss of cipitation carbon dioxide from water, which has been highly charged
Stalactites
with the gas and thereby dissolved large quantities of limestone.
In addition to widespread use as building material, limestone is used in the manufacture of cement, lime, and glass. It is used in many metallurgical processes to form a flux
with silica through the formation of calcium silicate. Strontium arid barium carbonates occur in nature as
strontianite,
SrCO 3 and
,
witherite,
BaCO
3,
respectively.
Next to the
sulfates,
these elements.
they are the most important sources of The stability of the carbonates toward
decomposition into the oxides increases, and the solubility in water decreases*with increasing atomic weight. The general solubility equilibria of these carbonates with acid is similar to those of calcium, discussed above. 9. Halides.-^Ptoe halides of beryllium, unlike most metallic Jaalides, are very poor conductors of electricity in the
fuêd state.
in solution,
salts,
"*
The beryllium
and the solutions upon evaporation

of the
halides are highly hydrolyzed yield basic

of the
^to>
The Buorides
members
group other than
beryllium are insoluble in water, even in the presence of an excess of fluoride ion. The fluorides of calcium, strontium,
and barium
crystallize in ionic lattices of the so-called
"calcium fluoride structure** (Append. V). Calcium fluoride occurs as the mineral fluorite or fluor-spar, and is important as the chief source of fluorine compounds. It is unusually transparent to ultraviolet light, nearly to 0.1 p. Jin the Dow process for extraction of magnesium from sea wat^r, the hydroxide is first precipitated by lime and then
convertect to chloride
by hydrochloric
acid.
The
chloride
crystallizes from its water solution at room temperature as MgCl 2 -6H 2 O. The anhydrous salt cannot be prepared from the hydrate, as upon heating it loses hydrogen chloride:
70
REFERENCE
[Ch.
2HC1. This reaction may be manufacture of hydrochloric acid. Magemployed nesium chloride combines with the oxide to form a basic
2
MgCl 2 +
H O = MgO +
for the'
2
The heat of the reaction, 20 kcal., indicates that the compound is very stable. This reaction is the basis for the Sorel cement which is now used extensively as a substitute for tile. Magnesium chloride is often present
chloride,
2.
Mg OQ
its deliquescent nature frequently causes the salt to "cake" in damp weather. This may be avoided by the addition of enough sodium bicarborfate to form the
in table salt,
and
basic
A number of double compounds of calcium chloride occur

as minerals, for example, tachydrite, CaCl 2 MgCl 2 42H 2 O, knd apatite, Ca 6 (PO4 3 Cl (or Ca 6 The chloride (PQ^3F). also be recovered from natural Wines and salt demay
<)
magnesium carbonate.
posits.
Below 30 the
heating
it
Upon
tetra-, di-,
salt crystallizes a& the hexahydrate. be dehydrated to form successively and monohydrates, and anhydrous salt. The
may
latter contains
some oxides formed through the

gen
chloride*,
loss of
hjj
as in the
160
of
magnesium chloride
cussed above. The soiubilit] relations of the various hydrates are given in Fig. 2.
The
eutectic of the hexahy-
drate
-60
60
100
and
ice
is
55
C.
di-
The anhydrous
160
salt
and
200
260
Parts of CaCI 2 per 100 Parts of H 2 FIG. 2. The system calcium
hydrate are used extensively as drying agents. The equilibrium pressure of water vapor for the reaction, CaCl 2
2
chloride
2
and water.
forms compounds with ammonia, CaCl 2 -8NH 3 and with alcohol, CaCl 2 4C 2 H 6O, and hence cannot be used for drying these substances; nor can it be used to dry hydrogen sulfide, which it de,
2H 2 O + 2H O = CaCl 2 4H O, is 3.78 mm. at 20. Calcium chloride
0.92
mm.
at
0, and
10]
GROUP
II.
71
composes somewhat with the evolution of hydrogen chloride.
FThe deliquescence
make
of (calcium chloride| and its low cost in sprinkling roads! Its high solubility and it useful
the low freezing point of its solutions render itUjsefulJri refrigerating brines. 7lts principal commercial sources are Ca(OH) 2 = 2NH3 ammonia^recovery plants, 2NH 4 C1
soda process
bj-product.
CaCl 2 + 2H 2 O|(see Ammonia, XI 6) and the Solvay 13), in both of which it results as a (cf. IV
Sarium chloride
is
prepared for use as an analytical resnt by beating a mixture of barium sulfate, calcium chloride, and carbon: BaSO 4 + CaCl 2 + 4C = BaCl 2 + CaS + 4CO. The chloride is leached out and purified by recrystallization,
frequently prepared for commercial use in the form of chloride. Both the chloride and bromide are more
is
Radium
insoluble than the corresponding barium compounds. r^flNf general tjje solubilities of the alkaline earth halides
increase in order of increasing atomic weight of the halogen.. and decrease with increasing atomic weight of the metal. .
10. Sulfates. Beryllium sulfate is very soluble, and forms syrupy liquids fjR&ni which it is difficult to crystallize a pure compound. The tetra- and hexahydrates have been obtained; the former is apparently unstable in respect to
the latter.
Magnesium
serite,
sulfate
is
fotind in
in the bittern of sea water.
mineral waters and It occurs as the minerals kie-
many
and epsomite (epsom salts), MgSCX 4 -H 2 O, Between 1.8 and 48 the rhombic heptahydrate a dodecahydrate crystallizes from solution; below 1.8 separates; and at higher temperatures there are formed a number of lower hydrates. The anhydrous salt cannot be prepared, due to formation of basic sulfates upon heating
MgSO
7H
O.
the hydrates.
Magnesium
sulfate
is
used in weighting a!id
sizing cotton, silk, paper,
and
leather; in fireproofing fabrics;
72
REFERENCE
[Ch.V
and
in medicine as a purgative, increase the secretion of bile.
and as a stimulant to
Calcium sulfate occurs in enormous deposits of gypsum, CaSO4'2H 2 O (when pure white called alabaster) and less
;
extensively as anhydrite, which is the anhydrous salt.

150
Plaster of Paris
The
ioo
63.6
phase in equilibrium with the saturated solution is gypsum below 63.5 C., and anhydrite above (Fig. 3). The solusolid
bility of the
50
two salts at the

point
is
transition
6 10 15 3 Moles xlO' of CaS04 per liter
0.015
mole per liter. The solubility of anhydrite decreases rapidly with rising
FIG. 3.
The system calcium

and water.
liter at
0.002 mole per
temperature and is only 150 C. This decrease in solubility is partly responsible for the separation of boiler scale f^tpi water containing calcium sulfate (Hard Water, Par. 11). A
second unstable and more soluble form of anhydrite also
sulfate
exists.
Upon
drate:
heating,
gypsum
loses
water to form the hemihy-
The 2 2 O. equilibrium pressure of water vapor reaches one atmosphere at 107 C. The hemihydrate is known as plaster of Paris.
2(CaSO 4 -2H 2 O) = (CaSO 4 ) 2 -H O + 3H
When
mixed with water the equilibrium is reversed, and the plaster sets to a mass of gypsum crystals. The setting results in an increase in volume, and the plaster thus In fills perfectly any mold into which it may be poured. of Paris the gypsum must not be heated too making plaster strongly, as the anhydrous salt is then formed which absorbs water very slowly. Such plaster is called "dead " burnt. The largest use of sulfate is in the manufacture
it is
of plaster for the interiors of buildings. Two varieties of plaster are made: (1) cement plaster, which is plaster of
10]
GROUP
II.
73
Paris to which glue, glycerine, and other organic substances have been added as "retarders" to prolong the time of setting; and (2) hard finish plasters, such as Keenes cement, which is made by the calcination of the anhydrous sulfate with alum or borax. This second type of plasters sets very slowly, but gives a hard finish. Large quantities of sulfate are used in the manufacture of stucco and wall board and The as a retarder for Portland cement (cf. XIV 23). yearly consumption of gypsum in the United States is about
six million tons.
There are two forms of the anhydrous calcium sulfate. is comparatively unreactive to water but the other, sometimes called soluble anhydrite, absorbs water rapidly. The latter is marketed under the trade name of "Drierite" as a highly efficient desiccant for gases and liquids. Water
One
remaining in air after drying with the reagent at 25 C. is said to be 0.005 mg. per liter. Strontium sulfate, SrSO 4 celestite, and barium sulfate,
,
heavy spar, are the most important minerals of these elements. These sulfates are extremely insoluble in water and dilute acids. They dissolve in concentrated sulfuric acid through the formation of HSO 4 ~, and are reprecipitated upon dilution. When the sulfate is treated with sodium carbonate solution, some of the sulfate is con,
BaSO 4
barite or
verted into carbonate
BaSO 4
+ CO
= BaCO + SO
3
At equilibrium the
barium
ratio of the molal concentration of
sulfate to carbonate for the
barium
salts is
about 0.01.
If
-MNa 2 CO
sulfate is treated, for example, with 100 cc. of 0.2 gram of barium carbonate will be formed. 3
,
By decanting the
solution
and repeating the treatment, any
amount of the sulfate may be converted into carbonate. The sulfate may also be converted into soluble salts by
reduction with carbon at about 800
to form the sulfide,
may then be dissolved in acid. Barium sulfate is slowly dissolved by boiling with concentrated HI, because of reduction of the sulfate by iodide.
which
74
REFERENCE
[Ch.
Barium sulfate is an important pigment. Lithopone, a mixture of barium sulfate and zinc sulfide, is prepared by the reaction: BaS + ZnSO4 = BaSO 4 + ZnS. This pigment has excellent covering power and does not darken with hydrogen sulfide. Precipitated barium sulfate is also used as a pigment, especially as an adulterant of white lead, but its covering power is not good. Barium sulfate is further employed as a "filler" in wall paper and in glazed It is taken internally in making X-ray photopaper. of the intestinal tract, on account of the opaqueness graphs to X-rays of such a heavy atom as barium. The sulfate is the only barium salt which may be used, as it alone is
sufficiently insoluble to prevent poisoning by the barium ion. Radium sulfate is even more insoluble than barium sulfate.
In the commercial extraction from uranium ores the

is
sulfate
and
precipitated along with those of barium and lead, converted into the chloride by either of the two methods
discussed above.
Water Softening. Water containing soluble calcium and magnesium salts is known as hard water. It is objec11.
tionable in the laundry because soap, which contains sodium or potassium salts of the higher fatty acids, such as stearic or palmitic acid (C^HssCOOH and Ci 5 H 3 iCOOH), forms This results insoluble salts with calcium and magnesium. in a waste of soap and the precipitate is a slimy curd which
is
difficult
to remove.
Hard water
is
objectionable in
The negaboilers because of the formation of boiler scale. tive ions present in hard water are principally chloride, sulfate, and bicarbonate. Upon heating to a high temperature
much
is
of the dissolved material
is
precipitated as scale
composed largely of anhydrite (Par. 10), calcium carbonate, and magnesium oxy-compounds. Such scale is a very poor conductor of heat, and its formation causes not only a waste of fuel, but also more rapid deterioration of the boiler through overheating at the surfaces where the heat is applied. Water which contains large quantities of
which
'11}
GROUP
II.
75
be softened simply by heating: Such water is re3 2 2 O. ferred to as possessing temporary hardness. In many industrial plants water is softened by the addition of lime equivalent to the calcium bicarbonate present, and sodium carbonate equivalent to the additional calcium and mag2HCO 3 ~ + 2OH- + 2Ca++ = 2CaCO 3 + 2H 2O, nesium:
bicarbonate
3
+ 2HCO ~ = CaCO + CO + H
may
and Ca++
+ CO ~ = CaCO
8
3.
In the zeolite or "pennutite" process water is softened by filtering slowly through artificial or natural zeolite, which
a hydrated sodium aluminum silicate. Although the composition varies somewhat in the different forms, NaH 6AlSiO7 may be written as an approximate formula.
is
The sodium
and other
is
replaceable by calcium, magnesium, ferrous, 2 ions. 2NaH 6AlSiO 7 Ca++ = Ca(H 6 -
2Na The equilibrium is reversible and when AlSiOr)2 the efficiency of the zeolite drops, it may be regenerated by
.
sodium
treating for a few hours with a concentrated solution of The process is inexpensive as only sodium chloride.
is
chloride
consumed.
The
zeolite minerals are
now
being replaced by solid syna) acids for cation ex-
thetic resins of
two general types:
from a water by the following reactions RH + Na+ + Cl~ = RNa + H+ + Cr and RNH 2 + H+ + OT = RNH 3 C1. By a combination of the two resin types, it is possible to produce a water of purity comparable with distilled water. The use of tetrasodium pyrophosphate, Na4 P 2 O 7 and hexasodium hexaphosphate, NaePeOig, is increasing in washing technology. These salts hold the calcium in solution and thus prevent the as complex ions, e.g., Ca 2 P6 Oi 8
:
,
,
change, b) bases (such as amine-formaldehyde resin) for anion exchange. Thus sodium chloride may be removed
the fatty acids, containwhich tend to precipitate the group ing the calcium in ordinary soap, a number of new detergents have been introduced which do not have this acid radical. The
formation of curds.
Since
it is
COOH
76
REFERENCE
[Ch.
sodium
3
salt of the sulfuric ester of cetyl alcohol,
and cetyl trimethyl ammonium (CH 3 ) 3 NBr, are examples. At a very high temperature the metals or 12. Carbides. The most their oxides react with carbon forming carbides. is calcium carbide, CaC 2 which is produced on a important large scale by heating a mixture of lime and carbon to a temperature of about 3,000 C. in an electric furnace: CaO + 3C = CaC 2 + CO. Calcium carbide reacts with water to form acetylene (cf XIII 18) CaC 2 + 2H 2 O
OSO Na
Ci 6 H 33 bromide, Ci6 H 33 -
2 2 2 may, therefore, be called calcium acetylide. Another important reaction of the carbide is the absorption of nitrogen at about 1,000 C. to form cy.
= Ca(OH)
+CH
It
anamide
(cf.
CaC 2 +
= CaCN 2 +
C.
'f his
reaction
is
the
basis for the
cyanamide
process for the fixation of nitrogen
XI
8).
13. Hydrides. Beryllium and magnesium do not readily form hydrides; but calcium, strontium, and barium react readily with hydrogen at high temperature (about 600). The large heats of the reactions, e.g., CaH 2 46 kcal.,
,
indicate the stable nature of these hydrides. Like the alkali hydrides, the hydrogen possesses a negative charge
salts.
molten Calcium hydride, although expensive, is an easily portable source of hydrogen for war balloons. One mole reacts with water to give two moles of hydrogen: CaH2
is
and
liberated at the
anode upon
electrolysis of the
+ 2H
soils.
= Ca(OH) 2
+ 2H
2.
a constituent of fertile by the electric arc process for the fixation of nitrogen (cf. XII 33). It as Ca(NO 3 ) 2 O at ordinary temperatures 2 crystallizes and is very soluble. Strontium nitrate is used in the manu14. Nitrates.
is
Calcium nitrate
The salt is produced
for use as fertilizer
4H
fire. Barium nitrate is the least soluble of the and is precipitated as the anhydrous salt upon the adgroup, dition of barium ion to solutions containing high concentrations of nitrate. It is sometimes used in making green fire.
facture of red
18]
GROUP
Sulfides.
II.
77
sulfides may be formed by the direct union of the elements, or by reduction of the sulfates by carbon. The compounds so prepared dissolve but slowly in water, but the apparent insolubility is merely a matter
15.
The
Solutions of these sulfides, like those of all soluble sulfides, are highly alkaline due to hydrolysis of the sulfide ion. Calcium sulfide is used as a depilatory. The use of barium sulfide has been mentioned in the preparation of lithopone. Both of these sulfides glow in the dark after exposure to sunlight, and are used in the preparation
of rate of solution. of luminous paint. This property is apparently due to the presence of traces of impurities, especially vanadium and
bismuth. In the regions about the particles of impurities, the crystal is able to absorb radiant energy through the
displacement of electrons to higher energy

rate at
levels.
The
which the electrons return to the stabler positions is slow, so that the absorbed energy is re-emitted over a period
of time.
16. Phosphates. The calcium phosphates are the most important of the group. They occur as the tri- and dicalcium orthophosphate, Ca 3 (PO 4 )2 and CaHPO 4 and as fluor and chlor apatites (Par. 4). Dried bones consist largely of calcium phosphate. Millions of tons of the insoluble tricalcium salts are treated yearly with sulfuric acid to convert into soluble acid phosphate, Ca(H 2 PO 4 ) 2 for
;
,
nium magnesium phosphate, NH 4 MgPO4 *6H 2 O, is important in analytical work (Par. 18). A number of com17. Other Important Compounds.
pounds containing the alkaline earths are discussed under other headings: bleaching powder (cf. X 14), glass (cf. XIV 22), cement (cf. XIV 23), asbestos (cf. XIV 19),
talc (cf. XIV 19). 18. Analytical Properties of Alkaline
use as fertilizer (see Superphosphate, XI
64).
Ammo-
Earth Ions.
is
The
comparatively chemistry of the alkaline earth simple, as they form no complexes with other ions (a few
ions
78
REFERENCE
[Ch.
exceptions with beryllium), and few insoluble compounds.
The ions are colorless. Beryllium ion has a sweet taste, magnesium ion a bitter taste, and calcium ion is practically tasteless. Be"*"* and Ba4^ are extremely poisonous. The
solubilities of the various
hydroxides has been discussed
(Par. 7). The solubilities of the chromate and sulfate decrease with increasing atomic weight; and likewise the
carbonate, with the exception that strontium carbonate
is
more
insoluble than barium.
The
beryllium, is separated from all the alkalies by taking advantage of the fact that they are not precipitated by a solution of ammonium sulfide. Amprecipitates CaCO 3 SrCO 3 BaCO 3 and about 30 per cent alcohol is present, MgCO3*(NH 4 ) 2 CO3. Radium is separated from barium by fractional crystallization of the chlorides, bromides, or chromates, the compounds of the latter being the more soluble. Barium may be separated from the lighter members of the group by the greater insolubility of the chromate. Strontium is separated from calcium in solution by the addition of a dilute solution of sulfate, which precipitates strontium sulfate but not calcium. Magnesium is separated from the heavier elements of the group through the solubility of the carbonate in
group, not including other positive ions except
monium carbonate
if
ammonium salts. The insoluble nature of beryllium hydroxide permits its ready separation from the remainder of the group. It may be distinguished from aluminum by the solubility of the beryllium hydroxide in excess bicarbonate, probably due to the formation of a complex bicar-
bonate ion. Calcium may be precipitated quantitatively as calcium

oxalate
cipitate
filtered
by the addition of ammonium oxalate. The preis composed of larger crystals, and is more easily
if
which
may ammonium
precipitated from a slightly acid solution, in somewhat soluble. The final traces of calcium then be removed by making the solution alkaline with
it is
hydroxide.
The
oxalate
may
be dried and
19]
GROUP
II.
79
weighed as such or ignited to form the carbonate:
= CaCO
;
CO.
Barium is usually precipitated and weighed as sulfate (cf. XI 34) while strontium may be determined as sulfate or
oxalate.
6H 2 O,
sium
is
Magnesium ammonium phosphate, NH MgPO 4 precipitated upon the addition of sodium phos4
phate and
salt.
formed,
ammonium hydroxide to a solution of a magneUpon ignition the pyrophosphate, Mg P20 is and may be weighed as such: 2NH 4 MgPO 4 *6H O
2
7,
= Mg P
2
+ 2NH +
3
13H 2 0.
spot test is a convenient method of distinguishing between calcium, barium, and strontium. One drop of an 0.4 per cent solution of the reagent is placed
The sodium rhodizonate
on a
filter
paper.
One drop
of test solution
is
placed on the
drop and then one drop of ethyl alcohol.
Barium and
strontium give red coloration. If the spot is now touched with one drop of Q.3N HC1, barium will remain bright red but strontium will dissolve.
Radium
sulfate
is less
soluble than
barium
sulfate.
The
separation of the two elements is accomplished by the fractional crystallization of the chlorides or bromides.
19. Spectra.
Beryllium and magnesium compounds do
not ionize sufficiently to impart color to the Bunsen flame. Volatile calcium compounds give a brick red, strontium a carmine, barium a yellow green, and radium a crimson flame. The coloration is very intense with the chlorides,
but
is
their
low
not satisfactory with the oxides or sulfates due to The electric arc spectra afford a volatility.
much more
delicate means of determining the presence of the alkaline earth elements, 0.002 mg. of calcium being The material to be analyzed is usually placed detectable. upon the positive pole of the arc. The wave lengths in
6 (10" mm.) of the more prominent lines are: calcium 423, 616; strontium 422, 461; barium 455, 493; magnesium 516.8 to 518.4, a group of three lines.
jLtju
Chapter VI
GROUP
1.
III.
BORON, ALUMINUM
The
is
groups, noble gas type, and a subgroup with kernels of the eighteen The elements of the main group are boron, electron type.
third periodic group, like the first and second divided into a main group with kernels of the
aluminum, scandium, yttrium, lanthanum (and Rare Earths), and actinium; those of the subgroup are gallium, indium, and thallium. Although the Rare Earths may be considered as members of the third main group, they constitute a family which is so unique from the standpoint of atomic structure that it seems advisable to discuss them in a separate chapter (cf. Lanthanide Series XXI). Because of the similarity of scandium, yttrium and lanthanum to the Rare Earths, the detailed consideration of these elements The elements above will be postponed to that chapter. atomic number 89 appear to have the same electronic structure as the Rare Earths, and actinium will be discussed
with that group (cf. Actinide Series XXII). , Boron is a nonmetal, but the remainder of the group are The melting points of the group are highly metallic. fairly high (Table I), and exhibit no regular trend from the
light to the
is
heavy elements.
An
oxidation state of
shown by these elements
in all of their
the exception of a few relatively boron. The oxides or hydroxides are less basic than those of the alkaline earth elements, as is to be expected from the increased charge on the positive ions. Boron oxide
80
compounds with unstable compounds of
2]
GROUP
distinctly acidic
III.
BORON, ALUMINUM
81
is
and shows only
faint basic properties.
Aluminum
oxide
is
amphoteric, while scandium, yttrium,
and lanthanum show no acid properties and are distinctly, though not strongly, basic. This increase in basic character of the oxides within the group is again to be correlated with
the increasing size of the ions of the heavier
?). (cf. in The elements
members
alkaline
less electropositive than the energies required to ionize the electrons from the gaseous atoms are very high, as
are
earth metals.
somewhat The
in
shown
hence the high values for the electrode potentials of the elements must be due to even greater energies of hydration of the positive ions. In the case of aluminum this is over a thousand kilogramfor
I
;
aluminum
Table
calories.
TABLE
BORON
of the earth's crust, estimated as
,
Boron constitutes but a small portion about 0.001 per cent. It occurs as boric acid, H 3 BO 3 and as borates. The principal deposits have resulted from the evaporation of inland seas.
2.
Occurrence.
In the Stassfurt area in
Germany
the deposits are chiefly
82
REFERENCE
[Ch.
VI
in the arid regions of western United States they consist largely of colemanite, Ca2B 6 On 5H2O, with some borax, Na 2 B 4 (V10H 2 O. Recently large deposits of kernite, Na 2 B 4O7*4H 2O, have been discovered
magnesium borates; while
Kern County, California. Boron is widely distributed in rocks in complex silicates and aluminates, such as tour2 MgNa9Al 3 (BO)2Si4O 20 maline,
in
Preparation and Properties. No satisfactory electrolytic method has been developed for the production of It is usually prepared by the reduction of the oxide boron.
3.
by powdered magnesium: B 2 O 3
2B; but other powerful reducing agents, such as sodium, may be used and the halides may be substituted for the oxide.
+ 3Mg = 3MgO +
The product of the reduction is amorphous boron, and, when magnesium is used, it is mixed with magnesium boride, Mg 3 B 2 the proportion of which may be minimized by using
,
excess of boric oxide, but in this case some suboxide, posremains. If this product is heated in an electric sibly B 3
furnace with an atmosphere of hydrogen a crystalline boron is obtained. When the reduction was first carried out with
to be crystalline boron, but further investigation has indicated that it consists of a mixture of aluminum borides, such as AlBi 2 Small crystals of boron have been prepared by the reduction of the trichloride with hydrogen when heated by a tungsten filament to a temperature around 1,500 C. The free element, as usually prepared, is a dark brown powder. The cooled fused material is brittle, almost as hard as diamond, and practically a non-conductor of electricity.
.
aluminum the product was thought
Reactions. Boron oxidizes slowly in air at 100 C., and burns at higher temperatures with a green flame. It ignites in fluorine at room temperature, and in the other
4.
halogens at higher temperatures. + 0.73 volt for the half reaction,
From
the potential
3H O
2
+B =H
BOa
+ 3H+
6]
GROUP
III.
BORON, ALUMINUM
83
the element should dissolve readily in acid. However no reaction occurs, the slowness doubtless being due to the large initial energy required to break the strong bonds in It does dissolve in fused alkalies due to the the solid.
stability of the borates.
It is readily oxidized
by strong
oxidizing agents, such as nitric acid, concentrated sulfuric It does not combine directly with hyacid, and ferric ion. drogen. These and other reactions are summarized below.
TABLE
4B 2B 2B 2B 2B
II
REACTIONS OF BORON
+ 3O = 2B O + 3X = 2BX + 3S = B $ + N - 2BN + 2NH = 2BN + 3H 2B + 6KOH - 2K BO + 3H - H BO + NO B + HN0 + H

2 2
Burns with green flame
With halogens At about 600 Above 1,200 Heated Fused with alkali
nB
-f-
mM
M m Bn
With a large number of metals
5. Oxides. Boron forms the oxide 8203, and there is evidence of suboxides BO or BsO. The sesquioxide may be prepared by heating boric acid to red heat. The product is a very hard, brittle glass. The oxide dissolves most metal oxides to form clear glasses. The sesquioxide takes up water rather rapidly to form the acid, and since it is otherwise
very non-reactive, it often serves as a convenient dehydrating agent. 6. Boric Acid and Borates. The addition of strong acids
boric acid, and this crystallizes from the water solution as the ortho-acid, 3 3
to borates liberates the
weak
H BO
solubility increases markedly with temperature; a saturated solution contains 2.6 per cent at 0, and 28.7 per cent at 100 C. The acid is somewhat volatile from hot solutions, possibly due to the formation of volatile hydrates. Upon heating, the ortho-acid loses water to form first the
The
and then the tetraboric acid, 2 B 4 O7 2 meta-acid, In water solution the ortho-acid acts as a weak monobasic
,
HBO
84
REFERENCE
its
[Ch.
VI
acid
i.e.,
reactions are those of the meta-acid,
HBO
2.
The
3
H BO
is
dissociation constant as calculated for the reaction, 10 = H+ The equilibrium 2 BO 3 ~, is 5.8 X 10~ 3
+H
complicated, above concentration of 0.5M by the formaThe acid is used in medicine, under the tion of 4 O7"~. name "boracic acid," as a mild antiseptic.
HB
Very few orthoborates are known, and

they hydrolyze
:
in
water solution
BO
Upon
+ 2H O = H BO
2
+ 2OH~
,
the addition of hydroxide to the ortho-acid the ~ is estab2HBO 2 = 2 O B 4 O7 equilibrium, 2BO 2 the equilibrium constant being about 10 3 The conlished,
stants for the

to
first
4
be about
.
10~~
and second ionization of H 2 B 4 O 7 appear and 10~9 respectively. Many of the meta,
borates are but moderately soluble,
e.g.,
Pb(BO 2 ) 2
10H 2 O,
With sodium hydroxide
AgBO Ba(BO the salt, Na B O

2,
2
2) 2,
borax, forms, and may be crystallized from the solution below 60 C. Above that temperature a pentahydrate is stable. The naturally occurring kernite, which is the tetrahydrate, is a metastable form and has not been
prepared in the laboratory. Borax is the most important compound of the element. It is but sparingly soluble at C., 1.3 g. per liter, but is very soluble at the temperature of transition to the pentahydrate. The solution is slightly alkaline by hydrolysis,
0.1
X 10~WOH~. Borax is from naturally occurring borates by (1) the extracprepared tion of the acid, and (2) the reaction of the acid with sodium
carbonate:
N solution containing about 2

3 2
4H 3 BO + Na CO 3 = Na B 4 O + 6H O + CO 2
2
7 2
form a glass which is capable of dissolving metal oxides, since it contains an excess of acid oxide,
fuses to
e.g.
Borax
Na 2O2B 2O 3 + CuO = Na 2OB 2O 3 + CuOB 2 O

its
3.
Upon
this
use in soldering and welding property depends to clean the metal surface of coatings of oxides. Many oxides dissolved in fused borax impart characteristic colors,
8]
GROUP
III.
BORON, ALUMINUM
85
the familiar borax bead tests (Append. VII). The colored glass finds use as artificial gems, and when ground, as pigments. Among other important uses of borax are the manufacture of glass, enamels, and soap, sizing for paper,
and as
a preservative for wood and meats. Besides the borates above mentioned there exist a very large number of polyborates, salts of the acids, (B 2 O 3 ) n is usually (H 2 O) m where n may be as large as six and
,
planar with the oxygens forming a triangle about the boron. In calcium metaborate the BO 2 groups form chains of triangles linked together by
3
one, two, or three. In boric acid the
BO
group
is
holding oxygen atoms in common, and in potassium metathe structure of the negative ion is, 3 B 3O6 borate,
o
i
</
7.
V\
i
.
tile
Boric acid forms with methyl alcohol the rather volamethyl borate, (CH 3 ) 3 BO 3 This compound burns with
ethyl borate is less basic nature of boric acid is slightly the reaction between boiling boric acid and phos-
a green flame.
volatile.
The corresponding
The very
shown by
3 BO 3 phoric acid to give boron phosphate, 3 PO 4 = BPO4 3H 2 O. Borax fused with ammonium chloride
+H
forms boron nitride: Na2 B 4 O 7 + 4NH 4 C1 = 4BN+ 2NaCl 2HC1. Boryl sulfate, (B0 ) 2 SO 4 is formed by + 7H 2 the action of sulfur trioxide upon boron trichloride. 8. Peroxyborates. Peroxyborates may be prepared by
O+
the action of peroxides upon borates or by the electrolytic oxidation of borate solutions. The most important of these compounds is the sodium salt, NaBO 3 *4H 2O. It is used as
86
REFERENCE
[Ch.
VI
a bleaching agent, and as an antiseptic constituent of certain tooth powders.

9.
Borides.
and aluminum have been prepared, among which the following may be mentioned: A1B 2 CaB 6 BaB 6 CB 4 SiB 6 ThB 4 CrB, 2 Fe 2 B, NiB, CoB. FeB, The so-called boron carbide, CB 4 may be made by the reduction of boric acid with carbon in the electric arc furnace. In spite of its great hardness, it may be cast and molded.
, , ,
, , ,
In addition to the borides of magnesium mentioned above, a large number of borides
WB
10. Halides.
liquids.
The halides are gases, or easily The melting and boiling points parallel
volatile
the cor-
responding values for the halogens.
They may be prepared by

fluoride
2
the direct union of the elements, but are usually formed from boric oxide, using hydrogen
in
the
+ 3H O; and
= 2BF 3 case of fluorine, B 2 3 in the case of the other halogens using the
O + 6HF
halogen and carbon at elevated temperatures: B 2 O 3 + 3C + 3X 2 = 2BX 3 + 3CO. The fluoride is used commercially as a catalyst, one of the more important reactions being the reaction of an alcohol and carbon dioxide at
high temperatures to form an organic acid. heavier halides are completely hydrolyzed
The
in
three
water:
3X~. The fluoride reand fluoboric acid: 4BF 8 + 3H 2 O = H 3 BO 3 + 3HBF4 Pure fluoboric acid is Boron fluoride unstable, but many of its salts are known. also forms a complex with ammonia, BNHaF 3 The prob3
2 3
3
BX + 3H O = H BO + 3H+ +
acts with water to form boric acid

.
electronic formulae of the fluoride, the complex, and fluoboric acid are, respectively:
able
ammonia
11]
GROUP
>
III.
BORON, ALUMINUM
87
TT J?
H:F:
B:F:
H:N:B:F
H:F:
F B F
: :
The molecule BH 3 does not exist but its dimer B 2 H 6 and other compounds of the series having the general formulas B n H n + 4 are well known. A few compounds of the series B n H n + 6 have also been prepared. The general 'name, boranes, is given to these hydrogen compounds. Some of the physical constants for the more important compounds are given in Table III.
11.
Hydrogen Compounds.
TABLE
III
PHYSICAL CONSTANTS OF THE BORANES
The boranes
of valence
are of unusual interest in the general theory
and chemical bonding since they are all short in the number of electrons required to give an electron pair to each bond. Various theories have been advanced to account for the electronic structures. In diborane two hydrogens appear to be located symmetrically between the two borons, and the assumption has been made that the bond between the boron atoms is a double electron pair with two The electron protons imbedded in the electron cloud. shortage and the suggested solution is illustrated below.
H H:B H
H
B :H
/ \/ \ H/
H
B
H
B
..
88
REFERENCE
[Ch.
VI
All of the boranes contain at least one of these "protonated
double-bonds/* Tetraborane
solution
12HC1 = B 4 Hio + H 2 + 6MgCl 2 Diborane is best prepared by a mixture of boron tribromide and hydrogen passing through an electric arc. The reaction is complex and
upon
may
be prepared by the action of an acid

boride.
magnesium
.
Mg B +
6
involves bromodiborane, diborane and boron bromide. Some of the more important reactions of diborane are
summarized
in
Table IV.
Many
IV
of the products of these
TABLE
REACTIONS OF DIBORANE
5B 2 H 6 = 2B 6 Hn + 4H 2 B 2 H 6 + 2Na = Na 2 B 2 H 6 B 2 H 6 -h HI = B 2 H 6 I + H 2 5B H 6 + B(CH ) = 6B 2 H5CH B 2 H 6 + 2CO = 2BH CO B H 6 + 2N(CH ) = 2BH N(CH ) 3B 2 H 6 + 6NH = 2B 3 N H 6 B 2 H + 3CH OH = 2BH(OCH 3 ) + 4H 2 3B 2 H 6 + 2LiC H 6 = 2LiBH + 2B H C 2 H 5 B 2 H 6 + H 2O = 6H 2 + 2B(OH) 3
2
3 3
3 3
reactions are also of considerable interest.
Sodium
salt of
di-
borane,
at 400
Na B H may
2
2
6,
be considered to be a
sodium
It is quite stable in dry air and sublimes but since it is a powerful reducing agent, it is lododiborane B2H 5 I reacts readily with highly reactive. sodium to form tetraborane: 2B 2 H 5 I + 2Na = B 4 Hi 2NaI. The chloro- and bromo-compounds may also be 137C. prepared. Borine carbonyl, H 3 BCO, melts at and boils at 64 C. It is in some respects similar to the volatile metal carbonyls (cf. XIX Lithium borohy15). ~ dride, LiBH 4 is a salt-like substance; the BH 4 radical 'is the negative counterpart to the positive radical 4+. A number of other metallo borohydrides have been pre-
ions with
B 2H6
C.,
NH
pared.
\iquid
Be(BH 4 ) 2
is
only slightly salt-like and the volatile

is
aluminum compound A1(BH 4 ) 3
even
less so.
12]
GROUP
III.
BORON, ALUMINUM
89
TABLE V
COMPARISON OF PHYSICAL PROPERTIES OF BORAZOLE AND BENZENE
heated with ammonia at a temperature This comof 250-300 C., the product is borazole, B 3 N 3 H 6
When diborane
is
is
remarkably simipound lar to benzene C 6 H 6 (cf. This is not surXIII 16).

since they contain not only the same number of atoms but also the same number of valence electrons i.e., boron with three elecprising
trons and nitrogen with five

electrons are equivalent to two carbon atoms with four
A comparison of some of the more imelectrons each.
.4
.8
1.2
Equivalents of NaOH portant physical properties FIG. 1. Titration curves for is given in Table V above. boric acid. Borazole, like benzene, has a ring structure and the vibrational frequencies of the two
are also remarkably similar. Like benzene the hydrogens of the ring may be substituted and a number of the methyl derivatives has been prepared.
The green flame test of methyl borate often employed as a qualitative test. The sample is olaced in a test tube, and sulfuric acid and methyl alcohol
12. Analytical.
is
90
REFERENCE
[Ch.
VI
added. The vapors which escape upon gentle warming burn with a green flame when ignited. Methyl orange does not react acid to boric acid, therefore soluble borates may be titrated with that indicator. Pure boric acid is difficult to titrate with a strong base,
as the equivalent point is highly alkaline as indicated in The addition of glycerol, mannite, or other polyalFig. 1. cohols which form complex ions with B0 2~, has the effect of
increasing the strength of the acid, and bringing the equivalent point into the range of phenolphthalein hence the acid
;
may
be titrated using that indicator.
ALUMINUM
Occurrence. Aluminum ranks third among the elein order of abundance. The estimated abundance in per cent in the igneous rocks is 8.13. It is the most
13.
ments
of the metallic elements. The most common minerals are the aluminosilicates, which include the feld2 KAl 3 (SiO 4 )3; and clays spars, as KAlSi 3 O 8 the micas, as (kaolin), as H 2 Al 2 (SiO 4 ) 2 H 2 O. Cryolite, Na 3 AlF 6 and bauxite, Al 2 O 3 raH 2 O, are important in the production of the metal. Ruby, sapphire, and corundum are forms of the
abundant
oxide.
Garnet is, approximately, [Ca, Mg, Fe]a[Al, Fe] 2 (SiO 4 )3; and turquoise, A1 2 (OH) 3 PO 4 *H 2 O, colored by copper phosphate.
14. Preparation.
mercially
The metal was first prepared comabout 1850 by the reduction of the chloride by
sodium at high temperature. Shortly thereafter methods were developed for the electrolysis of mixtures of molten aluminum, sodium fluorides, and chlorides, but the metal remained rare and expensive until the simultaneous .discovery by Hall and by H6roult of the electrolysis of the oxide in molten cryolite in 1886, which laid the foundation of the modern aluminum industry. In the Hall process,
the electrolysis
is
carried out in large iron pots with a thick
16]
GROUP
111.
BORON, ALUMINUM
91
carbon lining which acts as the cathode. A number of large amorphous carbon rods sticking down into the pot serve as anodes. The carbon rods are first lowered until they touch the cathode and an arc is struck; powdered cryolite is then added and melted by the heat of the arc. When a sufficient liquid bath is obtained, aluminum oxide is added and the anodes drawn farther away from the cathode.
The
addition of the oxide raises
somewhat the
resistance
The temperature of the bath is kept at of the liquid. abotit 1,000 C., and since this is above the melting point
of the metal,
cell
is liberated at and is the anode and gradually burns away the graphite. The cell reaction is: 2A1 2 O 3 = 4A1 + 3O 2 Ordinary commercial aluminum is about 99.0 to 99.5 per cent pure. It is
.
collects as a liquid in the drawn off at intervals. Oxygen

it
bottom
of the
very
difficult to refine
the impure metal, so the oxide
is
carefully purified before electrolysis (see Oxide). Recently, however, aluminum of 99.99 per cent purity has been made electrolytically from an alloy of aluminum, copper,
and
silicon.
The
cell consists of
three liquid layers of de-
creasing density; the lowest is the alloy, which is made the anode the middle layer consists of molten salts and the top layer is pure aluminum, which is made the cathode. Aluminum may be electroplated from a bath containing
; ;
aluminum chloride and bromide dissolved and benzene.

15. Properties.
2.7,
in ethyl
bromide
density
Its elec-
The metal
is
extremely
light,
and possesses
relatively high tensile strength.
conductivity is less than copper, but weight for weight it is twice as good a conductor. It is easily malleable and may be rolled into thin foil. It has a silvery appearance when freshly cut, but the ordinary surface has a dull white luster, since it is covered by a thin, firm coat of oxide which protects the surface from further oxidation. 16. Uses. In addition^to the common use in household utensils, the metal is becoming increasingly important in
trical
92
REFERENCE
[Ch.
VI
the construction of airplanes and other machines where Two important uses are as foil light weight is essential.
in place of tin
foil,
and as a "silver"
paint.
The
latter is
made by mixing the thin metal flakes with oil. Aluminum wire is used extensively in the United States, chiefly in
transmission
lines.
The metal
and
is
oxygen
holes.
in casting iron
It is also
steel,
used to remove dissolved and thus to prevent blow
used in "thermite" (Par. 17). The metal can be welded, brazed or soldered, but brazing is recommended as the solder lacks resistance to corrosive attack.
Alloys with Cu, Si, Mn, Mg, Fe, and Zn are important. The pure metal is difficult to work on the lathe as it sticks to the tools, but many of the alloys may be machined readily.
The
principal alloy used for construction purposes is Atcoa 4.5 per cent Cu, 0.6 per cent and 0.5 per cent Mg. Its tensile strength of 60,000 Ib. per sq. in. is
24S-T with
Mn
about double that of pure aluminum. "Binary" alloy, 2.5 per cent Mg and 0.25 per cent Cr, is another low magnesium alloy of importance. See also magnesium and
copper. 17. Reactions.
surface
it
Aluminum
is
is
protected so thoroughly
a very base metal, but its by its oxide coating that
may
be melted in air without serious oxidation.
How-
ever,
and
flash
at high temperatures the metal burns vigorously, aluminum powder and liquid oxygen unite with a
if
ignited with a match. in water unless the surface
The metal does not dissolve is amalgamated. The oxide
does not adhere to the amalgamated surface, and the metal is free to show its true electropositive nature by reacting with water or by oxidizing rapidly in air. The metal dissolves readily in hydrochloric acid, and slowly in sulfuric acid, but is rendered passive by nitric acid so that
this acid is often shipped in aluminum containers. solves rapidly in nitric acid, however, if a small of mercuric salt is present.
It dis-
amount
Nitric oxide
concentrated acid, and
ammonium
evolved from nitrate formed with

is
18]
GROUP
111.
BORON, ALUMINUM
93
Concentrated alkalies dissolve the metal with the dilute. evolution of hydrogen and the formation of the aluminate. The granulated metal reduces many oxides and sulfides
the so-called "Goldschmidt reaction." A mixture of aluminum and iron oxide, known as "thermite," The heat of the reaction is such that a is used in welding. is produced, and the iron of about 3,000 temperature
upon
ignition,
formed by the reduction can be run as a white hot liquid

into the crack to be welded.
To
start the thermite reaction
an ignition powder is required, such as a mixture of barium peroxide and aluminum. The aluminum electrode is highly irreversible, and exThe value, 1.67 tremely difficult to measure directly. is calculated from thermal data and indicates that volts, aluminum is almost as electropositive as magnesium.
The irreversibility of the aluminum electrode is made use of in rectifying alternating currents. When acting as anode,
the electrode has enormous resistance, but as cathode it has low resistance hence cells with an aluminum electrode allow one half of an alternating current to pass but not the other.
;
The
cell is
most
effective with
a phosphate electrolyte.
VI
TABLE
REACTIONS OF ALUMINUM
4A1 4- 3O 2 = 2A1 2 O 3 2A1 6H + = 2A1+++ 4- 3H 2 2A1 4- 2OH4H 2 O = 2H 2 A1O 3- 4- 3H 2 Al (amalgam) '4- 6H 2 O - 2A1(OH) 3 3H 2 Al (amalgam) 4H+ -f NO.,~ - A1+++ 4- NO -h 2A1 4- Fe2O 3 = AUOs 4- 2Fe
2H 2 O
Also forms
NH
2A1 4- 3X 2 = 2A1X 3 4A1 4- 6S = 2A1 2 S 3 2A1 4- N 2 = 2A1N 6A1 4- 3CO = A1 4 C 3 4- A1 2 O 3 = 1.67 Al - A1+++ 4-3eAi 4- 4OH- = H 2A1O 3 - 4- H 2 O
Analogous reaction with many oxides
With halogens At high temperature At high temperature At high temperature
3e~
E =
2.35
Oxide and Hydroxide. The oxide occurs in nature as corundum. When colored red it is called ruby, and
18.
94
REFERENCE
[Ch.
VI
when
iron
blue, sapphire. The color in the former is due to a trace of chromium, while that of the latter is attributed to
and titanium.
as emery.
When
Artificial
it
contains magnetite,
it
is
corundum, made by fusing the precipitated hydroxide in an electric furnace, is sold under the name "alundum," and artificial rubies and sapphires are now produced in large quantities. Corundum stands next to diamond and silicon carbide in hardness, and is used as an abrasive, and also in making refractory crucibles. The oxide is formed upon heating the hydroxide. Unless it has been ignited strongly, it will reabsorb water to form the hydroxide, and hence may be employed as a
known
drying agent.
Aluminum
hydroxide,
A1(OH) 3
exists in
gibbsite, stable below 155 C., and bayerite. also two forms of the hydroxy-oxide,
two forms There are

diaspore,
A1OOH
C., and bohmite, stable 155-280 C. Above 450 C. diaspore forms the metastable gamma alumina or the stable corundum. The freshly precipitated gel appears to be hydrous bohmite but gibbsite may be precipitated from aluminate solutions by acidifying with CO 2 The term bauxite is used for the commercial ores which are
stable 280-450
frequently largely bohmite. The hydroxide is amphoteric and the following are approximate values for the. dissociation constants:
A1(OH) 3 = A1+++ A1(OH) 3 = H+ +
K= + 3OHH AlO -(or A1O ~ + H O)

2 3
1.9
X X
10~33 10~13
.
The hydroxide
dissolved but slightly by ammonium hydroxide, especially in the presence of ammonium salt, to repress the concentration of hydroxide ion. The concentrations of hydroxide and hydrogen ions involved in
is
the precipitation and solution of the hydroxide are indicated in Fig. 2. Soluble carbonates, sul fides, acetates, and other salts of weak acids precipitate alumicyanides,
num
hydroxide by complete hydrolysis of both ions.
20]
GROUP
III.
BORON, ALUMINUM
95
The pure
of the metal
oxide required for the electrolytic preparation is made from bauxite or other hydrated oxides.
is first dissolved in sodium hydroxide to form a solution of sodium aluminate; and the hydroxide is then reprecipitated by passing in carbon dioxide, or by allowing the solution to stand in contact with crystallized A1(OH) 8
.
The mineral
In the latter case, the crystallized
and insoluble form

10
slowly precipitates (see Be-
10
Ppt. dissolves
Hydroxide). Many attempts have been made to Z prepare the pure oxide from J but no commercial 5 clay, process has yet been devel- 1 5
ryllifim
10
10
Rot,
com
)lete
10
Ppt. appears
oped.
19.
Aluminates. Sodium 10 and potassium aluminates are soluble but highly hydro40 20 50 10 30 cc. of Na OH lyzed. Most of the aluminates are, however, insoluble. FIG. 2. Precipitation and solution of aluminum hydroxide in alkali. The meta aluminates of the + 2 ions, (A1O 2 ) 2, occur as a mineral type known as spinels. Many complex aluminates exist, but few as simple ortho salts. The addition of ammonium hydroxide to a solution
aluminum and zinc salts precipitates aluminum hydroxide with some zinc aluminate. The formation of blue cobalt aluminate is mentioned under the analytical properties of aluminum. Calcium aluminate is an essential constituent of Portland cement (cf. XIV 23). 20. Halides. The anhydrous halides may be prepared
of
by the
direct action of the halogen upon the metal, while solutions of the halides are formed by the action of the
halogen acids upon the metal or hydroxide. Upon evaporation of the solutions, the halides may be obtained as highly hydrated compounds, e.g., A1C1 3 *6H 2 O. When heated, the hydrates hydrolyze completely to the oxide and the halogen
96
REFERENCE

The anhydrous
chloride
[Ch.
VI
acid,
which
is
evolved.
is
em-
ployed as a catalytic agent in many organic reactions. It sublimes without melting at ordinary pressures, the sublimation temperature being 183 at 750 mm. The
A1 2
aluminum halide gas molecules have the double formula, X6 and their structure may be represented as two tetrahedra of halide ions with an edge in common, and aluminum atoms at the centers of the tetrahedra.
XXX XXX
\Al/ \Al / / \ / \
The halides form compounds with ammonia similar in nature to the hydrates, thus A1C1 3 -6NH3 forms at ordinary temperatures by the action of ammonia gas upon the salt. Aluminum fluoride exhibits strong tendencies to form
complex
NaaAlFe.
nate,
salts,
giving the radical,
A1F6
as in cryolite,
These compounds are analogous to the alumi-
and owe their stability to the large value of the coulombic attaction of aluminum and fluoride ions. The tendency of the other halides of aluminum to form complexes decreases with increasing weight. 21. Sulfates. The sulfate, A1 2 (SO4 ) 3 18H 2 O, may be with difficulty from solutions at ordinary crystallized temperatures. It is highly soluble, and gives an acid solution by hydrolysis. A Q.25M solution is about 0.5 per cent
hydrolyzed, assuming that the hydrolysis reaction
is
Al"
"
1
4" 4"
+HO =
2
A1(OH)++
H+.
The
sulfate
is
prepared from
either bauxite or clay by treating with sulfuric acid. The latter reaction is: 3H 2 SO 4 = A1 2 (SO 4 ) 3 2 Al 2 (SiO 4 ) 2 -H 2
+ 2H
be
SiO4
+H
O.
The
silicic
acid
is
insoluble,
and may
filtered off.
and with ammonium, silver, and thallous sulfates, aluminum sulfate forms isomorphous compounds of the general type, MA1(SO4 ) 2 -,
alkali sulfates, except lithium,
With the
21]
GROUP
III.
BORON, ALUMINUM
97
12H2O, known as alums. The class is even more general, and the aluminum may be substituted by Fe^*" 0+++, 4" and other + 3 ions. The tendency of the Mn~HH~, Ti^ elements to form alums increases with increasing alkali atomic weight; cesium forms more alums than the others and these are in general less soluble. The ammonium and potassium alums are the most important commercially. These alums are very soluble in hot water, but much less in cold, so that they may readily be purified by crystallization.
1
",
",
Crystal structure data indicate that six of the water molecules form an octohedran about the aluminum ion and the other six water molecules occupy "cavities" in the
lattice.
The
principal uses of
aluminum
sulfate
and alum dethe

(1)
hydrolysis pend primarily upon ion, and may be divided into two classes:
the
of
aluminum
those de-
pending upon properties of hydrogen ion, and (2) those depending upon the properties of aluminum hydroxide. In the first class may be mentioned the use in baking powder to furnish acid to cause the liberation of carbon
dioxide.
extinguishers, in
reaction is employed in certain fire which solutions of alum are caused to react with solutions of sodium bicarbonate containing
The same
To
organic substances capable of forming very stable foams. the second class belong the uses as a mordant in dyeing,
and as a clarifying agent for water. Aluminum hydroxide, formed by the addition of sodium carbonate or lime to alum or aluminum sulfate, is a very good absorbent for certain dyes, and also attaches itself to the fiber, thus Mordants of serving to bind the dye to the material.
this nature are frequently necessary in Certain dyes may also be adsorbed on
dyeing cotton goods.
aluminum hydroxide to form pigments known as "lakes." The action of alum in water clarification is again due to the adsorption of suspended material by the gelatinous precipitate. Alum is also used in sizing paper and in fireproofing fabric.
98
REFERENCE
[Ch.
VI
When
heated
it
loses
product,
known
as "burnt alum,"
water and some sulfur trioxide; the is used in medicine as
an "astringent."
22. Ultramarine.
complex sodium aluminum
silicate
and
sulfide occurs in nature as the mineral lapis lazuli.
When
ground,
it is
constitutes the blue pigment, ultramarine.
The pigment
now manufactured by
heating a mixture
of clay, sodium sulfate, and carbon, and is much used for laundry blue, as a water color, and in neutralizing yellow It is tones in linen, ctarch, paper, and granulated sugar. stable toward alkalies, but evolves hydrogen sulfide with
acids.
23.
A^Ss,
Other Compounds of Aluminum. Aluminum sulfide, is formed by the reduction of metallic sulfides by
It is completely hydroat high temperatures. Aluminum acetate, A1(C 2 3 2 )3, has many lyzed in water. It may be prepared uses similar to those of the sulfate.
aluminum
HO
from the sulfate by metathesis with barium acetate. Kaolin, the hydrated silicate, is further discussed under
silicon.
24. Analytical Properties of
Aluminum
Ion.
Aluminum
ion
It
is colorless,
and has a
slightly bitter astringent taste.
forms an insoluble amphoteric hydroxide as already The orthophosphate, A1PO 4 is insoluble, and discussed. precipitates upon the addition of a soluble phosphate and
,
ammonium
of
hydroxide to aluminum ion.
The
separation
aluminum from other

is
as the hydroxide,
its identification positive ions, outlined in the general scheme of
and
analysis (Append. VI). Precipitated aluminum hydroxide is often confirmed by moistening the precipitate with a drop of cobalt nitrate solution and igniting at red heat.
A
of
blue residue (cobalt aluminate) indicates the presence
aluminum. The test is capable of detecting 0.2 mg. aluminum. It is necessary in carrying out the test to have the aluminum oxide in excess, as otherwise the color
of
observed
is
obscured by the black cobalt oxide.
The
test
24]
GROUP
if
III.
BORON, ALUMINUM
salts are
99
is
not satisfactory
sodium or potassium
occluded
in the precipitate in any large amounts. The formation of a bright red lake (cf. Par. 21) with the 4 salt of aurin tricarboxylic acid) may dye aluminon
(NH
aluminum. satisfactory method of carrying out the test is to use an aluminum free filter paper treated with a dilute solution of the dye and amalso be used to detect
drop of test solution is placed on the paper and held for a few seconds in the fumes from an ammonivim hydroxide bottle. Red color indicates aluminum. Complex aluminates may be dissolved by fusion in a platinum dish with potassium acid sulfate or with sodium carbonate, followed by extraction with hydrochloric acid.
acetate.
monium
removed by evaporating to dryness, boiling again with hydrochloric acid, and filtering. Aluminum is generally determined in quantitative analSilica is
ysis
by precipitating as the hydroxide and weighing as the oxide.
Chapter VII
SUBGROUP
1.
I.
COPPER, SILVER,
AND GOLD
of Subgroup I, copper, Cu (cuprum), (argentum), and gold, Au (aurum), differ markedly in properties from the elements of the main group. Unlike the alkalies they are "noble" metals and are not This property may be correlated (cf. readily oxidized. Ill 6) with the higher boiling points of the metals, indicating greater difficulty in separating their atoms from each other, and with the larger ionization potentials of the 2 O, gaseous atoms (Table I). Their oxides, of the type are much less basic than the alkali oxides, a fact which is related to the smaller size of the ions (cf. Table I, also HI 7). These elements also form certain compounds in which they have oxidation states greater than + 1; in fact, the ions of + 2 copper and + 3 gold are in general
The elements
silver,
Ag
more
stable in respect to reducing agents than the ions of 1 state. the The outer electron shell of the kernel is not of the noble gas type, but contains 18 electrons, and
these higher states exist through the possibility of removing one or two electrons from this shell. This process is
impossible in the case of the main group elements, since the energies of their kernel electrons are very much greater. 2. The ions of the subgroup elements possess the prop%
erty of forming very stable complexes, such as

2 ~~,
Cu(NH
"
3) 4
f "h
,
AuCl 4 ~. This property is in general strongly Ag(CN) exhibited by all ions with more than eight electrons in the
outer shell of the kernel, and
may
be considered as due to
100
2]
SUBGROUP
I.
COPPER, SILVER,
AND GOLD
101
the ability of these positive ions to form definite electron These complexes have been called coordinapair bonds.
tion
compounds, and the number of groups or ions held by the positive ion is termed its coordination number. The electrons of the bond are of course supplied by the
coordinating group.
:N
-9.
Cl
Ag
*
Cl
"
Au
Cl
C
:N
:
H H N H
:
H H:N :H "
:
H
N H
:
Cu
ii
H:N :H
H
Silver cyanide ion
Chloraurate ion
Cupric ammonia ion
ionic
Fluoride ion, which exhibits strong tendencies to form complexes with the smaller ions such as aluminum,
does not readily form complexes with the subgroup elements, because its electrons are held so firmly that they are not readily shared in bond formation. The stability of
the complexes and also the solubility of the compounds of the ions appear to be related to the electrical distortion or polarization of the negative ions. This relation is
illustrated
of a
by the following comparison of the solubilities number of silver salts with the indices of refraction
which
of the negative ions,
may
be taken as a measure of
the polarization.
eral to those for covalent
Moreover, the interatomic distances correspond in genbonds (cf Appendix) rather than
.
102
REFERENCE

~
[Ch.VII
those for the ionic radii. Both the AuCl 4 and Cu(NH 3 )4 ++ given above are square planar structures instead of the customary tetrahedra, which result from a combination of s and p orbitals. The square structures are formed by a
combination of one s, two />, and one d orbitals. 3. The basic nature of the oxide (comparing the + 1 oxides) increases with increasing size of the atom, but the
electropositive nature of the metal, i.e. ease of oxidation, decreases; gold being one of the most noble metals. The
metals are
all
excellent electrical conductors.
COPPER
state.
Occurrence. Copper frequently occurs in the free As a rule such deposits are small, but in the Lake Superior region masses of native copper have been found weighing many tons. The copper ores may be classified as: (1) sulfide ores, the more important being chalcopyrite,
4.
CuFeS 2
bornite, approximately
Cu 5 FeS 4
chalcocite,
Cu 2 S,
and indigo copper, CuS; (2) oxidized ores, consisting of the oxides and their compounds with negative elements, such as cuprite, Cu2O, melaconite, CuO, malachite, Cu 2 (OH) 2 -
Cu 3 (OH) 2 (CO 3 ) 2 chrysocolla, CuSiO 3 -2H 2 O, and atacamite, CuCl 2 3CuO-3H 2 O. The average percent3,
CO
azurite,
4 age of copper in igneous rocks is estimated as 1.0 X 10~ 5. Metallurgy. The methods employed in winning copfrom its ores vary greatly with the type of ore. With per native copper the rock is crushed, the copper concentrated
.
by mechanical methods, and the metal purified by melting with a flux to remove the remaining gangue. High grade
by heating in a furnace with a mixture of coke and suitable fluxes. Low grade ores may be worked by extraction of the copper with ammonia or other solvents. About 70 per cent of the copper in the United States is produced from sulfide ores. The procedure is somewhat complicated because the sulfide is not
oxidized ores are smelted
5]
SUBGROUP
I.
COPPER, SILVER,
AND GOLD
103
TABLE
readily reduced, and also because of the difficulty in removing the large amount of iron which is always present. The steps in the process are (1) concentration of the ore
(only with low grade ores), (2) roasting, (3) formation of M "copper matte, largely Cu2S and FeS, (4) reduction of " " the matte tp blister copper/' (5) refining of the blister
copper/' The concentration of low grade ores is now usually carried " out by the flotation* methods. The ore is ground with oil and water. The sulfide particles are wet by the oil
'
and the earthy

to a larger
and
The mass is added particles by the water. of water containing a foaming agent beaten or blown into a foam. The sulfide particles
amount
and are carried
off
collect at the surface of the bubbles
with the foam, while the earthy particles, or "gangue," settle to the bottom. It is claimed that the method will
104
REFERENCE
[Ch. VII
remove as much as 95 per cent of the metal from an ore containing as low as 2 per cent copper. The roasting step serves to remove volatile oxides of arsenic and antimony, and to oxidize part of the sulfides to the metallic oxides and sulfur dioxide. The next step is the formation of the copper matte by heating the ore
with addition of sand or calcium carbonate in the proper proportion to form easily fusible calcium silicate slag. This is carried out either in a reverberatory furnace in which hot flames of burning coal dust are played upon the surface of the charge, or in a blast furnace where a blast of In the latter case coke air is blown through the charge. is added to the mixture, and its combustion supplies the The temperature is kept high enough to melt the heat. charge, and the heavier mixture of the molten sulfides settles beneath the lighter slag. During the process, some
of the iron
is
is
removed as iron
sulfides.
silicate,
and some
of the sulfur
oxidized to sulfur dioxide.
The matte
consists of cuprous
step is now generally carried out in the so-called copper converter, a barrel shaped vessel provided with a number of blast pipes. Air
and ferrous
The next
blown through the charge, to which sand has been added, and the ferrous sulfide is converted to ferrous oxide, which forms ferrous silicate: 2FeS + 3O 2 = 2FeO + 2SO 2 and FeO + SiO 2 = FeSiO 3 When the iron sulfide is all oxidized, the blast is stopped and the slag poured off. The blast is then renewed and metallic copper formed by the oxidation of the sulfur: Cu 2 S + O 2 = 2Cu + SO 2 The copper is poured into molds, and upon cooling evolves some " dissolved sulfur dioxide, which gives the surface a blisis
,
tered" appearance. About 70 per cent of the blister copper in the United States is refined by the electrolytic method, wherein the
crude metal
is made the anode in a cell containing an acid thin plate of pure copper solution of copper suifate. serves as the cathode. By regulating the potential drop
6]
SUBGROUP
I.
COPPER, SILVER,
AND GOLD
105
across the cell, it is possible to dissolve copper and the baser metals at the anode, leaving behind the more noble metals, such as silver, gold, and platinum as an "anode sludge/' The difference in the electro-potential of copper and the base metals, iron, zinc, lead, and nickel, is sufficient so that in the acid solution copper is preferentially deposited at the cathode with a purity of approximately 99.9 per cent. In the older methods of refining blister copper, the metal is heated in a silica lined vessel, with agitation to bring about oxidation of the base metals by the air. The basic oxides then form a slag with the silica lining. The principal impurity now present is cuprous oxide which is soluble in molten copper so after skimming off the slag, the metal is stirred with a pole of green wood, and the hot hydrocarbons liberated from the wood reduce the cuprous oxide. The process does not give as pure copper as the electrolytic method, nor does it render possible the recovery of the more noble metals.
;
6.
The Metal.
are given in over two million tons, of which the United States produces about 40 per cent. Its principal use, due to its high electrical
The more important physical properties Table I. The yearly production of copper is
conductivity and good ductility, is in electrical transmission. For this purpose it must be extremely pure, since the presence of a few tenths of a per cent of certain impurities, especially arsenic, greatly increases the resistance. Because of its high thermal conductivity and comparative inertness, it is used in boilers, water heaters, cooking utensils, steam
used in the electrotyping processes now generally employed in reproducing engravings and printing books. A plaster or wax cast is made of each page of type, the cast is coated with graphite to render it conducting, and copper is then deposited upon the cast electrolytically. The deposit of copper is then removed and strengthened by filling the back with lead. A summary of the composition of the more important
pipes, etc.
It is
106
REFERENCE
[Ch. VII
is given in Table II. Bronze is much harder than copper, and also more readily cast into molds. Aluminum bronze resembles gold in color, and is used in gilt paint. Aluminum silicon bronze is quite resistant to corrosion and has a tensile strength about double that of pure copper. Brass foil is often used as a substitute for gold leaf.
alloys of copper
German
silver, as its
name
indicates, resembles silver in
appearance. It is a very poor conductor of heat. Phosphor bronze is employed in bearings. Constantan has a high and
very reproducible thermoelectric force against copper, and the copper-constantan thermo-couple is used in the measurement of temperature.
TABLE
^rass
/Bronze
II
COPPER ALLOYS
60-90 Cu, 10-40 Zn 80 Cu, 15 Sn, 5 Zn 90 Cu, 10 Al 91 Cu, 7 Al, 2 Si 80 Cu, 10 Sn, 9 Sb, 1 P 70-95 Cu, 5-30 Mn 95 Cu, 5 Si 90 Cu, 10 Sn 78 Cu, 22 Sn 60 Cu, 40 Ni 82 Cu, 15 Mn, 3 Ni 52-60 Cu, 25 Zn, 15-22 Ni
2.5 Be, 97.5
Aluminum bronze Aluminum silicon bronze

Phosphor bronze
Manganese bronze
Silicon bronze
Gunmetal
Bell metal ^Constantan
Manganin
German
silver
Beryllium alloy
Cu
TABLE
2Cu 4Cu
III
REACTIONS OF THE METAL
Cu
+ O = 2CuO + O = 2Cu O + F = CuF

2 2
2 2 2
Rapid at about 300
At about
1,000
.
2Cu
+S
-f
= Cu^
-f
3
Also with C1 2 and Br 2 I2 forms Cul. Also with Upon heating

Se, Te,
P
acid not too
Cu Cu
+ 2H+
2
4NH 2Cu -f O + CO
JO 2 - Cu+ f + H 2O + iO 2 + H 2O = Cu(NH 3)4(OH)j

2
With any
weak
-f
H O = Cu CO
2 2
(OH)2
2
Corrosion in air
Cu 4- 2H 2SO 4 Cu = Cu ++ +
CuSO 4
2e~
+ SO + 2H O
2
Hot
In
cone, acid
general with oxidizing agents of potential greater than 0.34 volt
7]
SUBGROUP
I.
COPPER, SILVER,
AND GOLD
in
-|07
7.
Oxidation States.
is
Copper forms compounds

1
its
oxidation state
(cuprous),
2 (cupric),
which and (a
few unstable compounds) + 3. Important potential values dealing with the oxidation and reduction of cuprous and cupric compounds have been summarized in Table IV.
TABLE
IV
OXIDATION REDUCTION POTENTIALS OF COPPER
+ S = Cu S + 2e= CuS + 2e~ Qu + S 2Cu + 2OH- = Cu O + H O + 2e~ CNS- + Cu - CuCNS + e~ 2e~ Cu + 2OH- = Cu(OH) Cu + I- = CuI+<r 2NH 4- Cu = Cu(NH + 2<r = 2Cu(OH) + Cu O + 2OH- + H 4NH + Cu = Cu(NHs)4+ + + 2er Cu + Br- = CuBr + e~ Cu + Cl- = CuCl +e~ Cu+ = Cu ++ + e~ Cu = Cu++ + 2eCu = Cu+ + e~ CuCl = Cu++ + Cl- + e~ Cul = CU++ + I- + e~ Cu ++ = Cu +++ + e~
2Cu
2
2
VOLTS26
+ 0.95 + 0.76
-f 0.36
-f-
+ 0.27 + 0.21
+0.19 +0.11
2<r
4-
3) 2
+ 0.09 + 0.05
- 0.03 - 0.12 - O.ir - 0,34 - 0.52 - 0.57

-0.88
1.8
it
In the case of soluble salts giving the ions Cu + and Cu"*" ", is easier to oxidize the metal to the cupric state than to
1
the cuprous, and this also means that the equilibrium, Cu^ 4", favors the reactions as written: e.g. 2Cu + = Cu
cuprous nitrate will decompose into cupric nitrate and copper. Also the reduction of cupric ion in such solutions will yield the metal and not cuprous ion. However, cuprous ion forms many very slightly soluble salts and very stable complex ions, and with many of these the above equilibria are reversed. The following are a number of important examples (a) Halides. Cupric chloride and bromide are reduced,
:
by electrolysis or by the metal, to the cuprous salt. addition of iodide to cupric ion results in the liberation of iodine: Cu++ + 21- = Cul 4I 2
e.g.
The
108
REFERENCE
[Ch. VII
(6) Cyanide. Cupric ion and cyanide give cuprous cyanide ion and cyanogen (or cyanate in ammonia solutions)
2Cu++
This complex is 8 2 will dissolve in hydrogen cyanide, so stable that the metal in spite of its weakness, with the evolution of hydrogen:
2.
+ 8CN- = 2Cu(CN)
~+CN
+ |H
2.
Cu + 3HCN =
(c)
Oxide.
H 2 Cu(CN) 3 The reduction
of cupric
compounds
is
in alka-
line solution gives
cuprous oxide,
Cu 2 O. This
the basis
for the
common
4
6
alkaline
4
test for sugar (specifically dextrose). An solution of copper sulfate and Rochelle salts,
2
as Fehling's solution, will give a red coloration with extremely small quantities of dextrose, due to the precipitation of Cu 2 O. (d} Reduction upon Heating. Cupric compounds are in
NaKC H O 4H
O,
known
general unstable in respect to the cuprous
upon heating.
oxygen be-
2CuO = Cu O + |O 2 The
2
.
partial pressure of
comes appreciable above 900 C. However, the two oxides appear to form a solid solution in each other so that the partial pressure depends both upon the temperature and the concentration of the two oxides. Cupric sulfide decomposes at red heat 2CuS = Cu 2 S + S. The cupric halides decom:
2 pose according to the equation: 2CuX 2 = 2CuX + fluoride decomposes around 500, and the chloride Cupric and bromide at somewhat lower temperatures. The iodide is not stable even at room temperatures. 7. Powerful oxidizing agents, in alkaline solution, oxidize copper to the + 3 state, probably forming CuO 2 ~~. The calcium salt may be precipitated. This compound is very
.
unstable;
it
tends to evolve oxygen and
it
reacts readily
Cuprous Compounds. Cuprous compounds are prepared from the cupric by methods based upon the reactions discussed in the preceding paragraph. The ion, and in general its complex ions, are colorless. The oxide occurs in nature. It has a fine red color, and for that reason is employed in making ruby glass and in coloring
with reducing agents. 8. Cuprous Ion and
9]
SUBGROUP
I.
COPPER, SILVER,
AND GOLD
109
For the arrangement of the ions in the crystal Appendix V. It is insoluble in water and alkalies. Alkalies precipitate yellow orange hydrous cuprous oxide from cuprous compounds. Upon heating, it is transformed to the red modification. It reacts with sulfuric, nitric, and hydrofluoric acids to give copper and the cupric salt. It dissolves in ammonia, alkali cyanide, and hydrochloric acid to form the complex ions: Cu(NH 3 ) 2 + Cu(CN) 3 and CuCU". The cuprous chloride and ammonia solution is Oxidized by oxygen to the cupric compound, and advantage is sometimes taken of this in removing oxygen from gas:
porcelain.
lattice see
,
,
2Cu(NH
3) 2
+ 2NH OH +
4
K> 2 = 2Cu(NH 3 ) 4 + +
+ 2OH~
slightly
+H
O.
The
chloride, bromide,
and iodide are
soluble in water, the solubility decreasing in the order given, as with the corresponding silver halides. They are all soluble in excess of the halide ion: e.g. CuBr Br~ = CuBr 2 ~. The chloride is hydrolyzed in boiling water: 2CuCl 2
+HO
= Cu + 2H + + 2C1~. A solution of chlorocuprous acid, HCuCl 2 is employed in gas- analysis to absorb carbon mon2
,
oxide.
reaction is apparently due to the formation of a rather unstable carbonyl cuprous chloride, CuCl-CO 2H 2 O. A solution of cuprous ammonia carbonate is sometimes employed in place of the chloride for the same pur-
The
The chloride is soluble in cyanide and in ammonia, with the formation of the complex ions. The cyanide ion, Cu(CN) 3 gives the smallest concentration of cuprous ion of any of the cuprous compounds. Cuprous sulfide is formed
pose.
,
by heating together copper and sulfur, by roasting cupric sulfide, by reduction of cupric sulfide by hydrogen, and by Like precipitation with H 2 S from solutions of CuCl 2~".
many
lattice
sulfides its composition
may
contain
many
not constant as the crystal holes with either of the ions

is
missing.
9.
Cuprous thiocyanate
is
also insoluble.
Cupric Ion. Cupric ion in dilute aqueous solution " H probably exists as Cu(H 2 O) 4 ", and the characteristic blue
color of its solutions
is
probably due to this complex.
Its
110
REFERENCE
[Ch. Vll
slightly soluble compounds are the black the green hydroxide, Cu(OH) 2 the green basic carbonate, Cu 2 CO 3 (OH) 2 the black sulfide, CuS; and red-
most important
oxide,
CuO;
brown ferrocyanide, Cu 2 Fe(CN) 6

complex
ions
f4
3 )4"
";
The most important

cupric
are
the
deep
blue
ammonia,
,
Cu(NH
chlor and
brom
cuprates,
CuCl 4
CuBr4
Cu-
(respectively
green
and
brown);
and
tartrate,
(C 4 H 4 O 6 ) 2
all slightly
acid
The by
soluble cupric salts of strong acids are
hydrolysis.
10.
Cupric Oxide and Hydroxide.
The
addition of hy-
droxide ion to a cold solution of cupric ion gives a light bluish green gelatinous precipitate of the hydroxide, but in hot solutions the black oxide is formed. The oxide does not
absorb water to form the hydroxide.
weak
It is
base.
Cu(OH) 2 = Cu++
The hydroxide is a 2OH~, K = 5.6 X 10~20

.
not soluble in dilute alkalies, but does dissolve somewhat in 6N to 18JV NaOH, forming deep blue solutions of
+ 2H 2O, K = 1.2 Cu(OH) 2 + 2OH- = Cu0 2 3 X 10~ The sodium cuprate, Na 2 CuO 2 may be precipitated from the concentrated alkaline solutions. The
cuprate,
.
,
hydroxide, forming the forming the comcomplex ammonia ion, and plex tartrate (Fehling's solution). The oxide is also formed by heating the carbonate or nitrate. At moderately high
hydroxide
is
soluble in
ammonium
in tartrate,
temperatures, it oxidizes hydrogen, forming water and copper. In quantitative organic analysis, mixtures of the oxide and organic compound are heated to effect the oxidation of the combined carbon and hydrogen to carbon dioxide and
water.
11.
Cupric Halides.
are readily soluble.

stable.
The fluoride, chloride, and bromide As mentioned above, the iodide is unsolution of the chloride
is
The concentrated
green,
of the bromide, brown. The color appears to be due to existence of part of the copper in the complex ions, CuCl 4
and
(green), and CuBr4 (brown). Upon electrolysis, copper moves toward both the cathode and anode. When the con-
14]
SUBGROUP
I.
COPPER, SILVER,
AND GOLD
T1
centrated solutions are diluted, the blue of the again predominates. The solid halides absorb ammonia gas to form compounds, suchasCuCl 2 -6NH 3 These compounds, of course, give the complex ammonia ion upon solution.
.
12.
Cupric Sulfate.
salt.
copper absorbs water to form the blue pentahydrate,
The sulfate is the most important The anhydrous salt is colorless, but it readily
as "blue vitriol."
5H 2 O, known
The
five
CuSC>4 molecules of
water of hydration may be successively replaced by ammonia. The sulfate is prepared commercially by roasting the sulfide, either to form the sulfate, which may be extracted with water, or to form the oxide, which may be dissolved in sulfuric acid. A Q.2N solution is 0.057 per cent
hydrolyzed at 25 C. From solutions of copper sulfate and the alkali sulfates, double salts, such as K 2 Cu(SO 4 ) 2 6H 2O, may be crystallized. Upon slow addition of alkali to copper sulfate solution, a number of insoluble basic sulfates are
formed, for example, Cu5(SO 4 ) 2 (OH) 6 2H 2 O. Basic sulfates,
made by mixing copper sulfate and slaked lime, are used under the name of "Bordeaux mixture" as a fungicide.
Copper sulfate is used in calico and electrotyping, and as an
battery.
pecially
13.
printing, in electroplating^ electrolyte in the gravity
Copper is very poisonous to lower organisms, esalgae, and is used in swimming pools and water
works to prevent the growth

Cupric Sulfide.
is prethe action of hydrogen cipitated from cupric solutions by sulfide, even in the presence of high concentrations of acid.
The brownish black
of such organisms. sulfide
When
some cuprous
precipitated from neutral solution, it may contain sulfide. It is soluble in hot 2N HNOs because
of the oxidation of the sulfur, . the formation of Cu(CN) 3

in
and
in
cyanide ion because of
The
sulfide is slightly soluble
ammonium polysulfide, probably through the formation of thiocuprates. 14. Other Cupric Salts. The nitrate crystallizes as blue
hexahydrate.
Because of the smaller solubility of the hy-
<12
REFERENCE
[Ch. VII
droxide, the normal carbonate does not exist, but two basic carbonates, azurite, Cu 3 (CO 3 )2(OH)2, and malachite, Cu 2 -
CO3(OH) 2 occur
,
in nature.
The
latter is the green coating
which forms on copper vessels through the action of oxygen and carbonic acid of the air. A basic acetate, verdigris,
It is used as a green pigment. formed by the action of air upon copper in the presence of acetic acid. A mixed acetate and arsenite, Cu 4 (C2H3O2)2(AsO 3 )2, Paris green, is used as an insecticide. Copper ferrocyanide, Cu2Fe(CN) 6 may be formed as a brown gelatinous precipitate. It has been used in the preparation of semi-permeable membranes for studying osmotic pres3 2,
Cu (C2H 3 02)4(OH)
is
sure.
Copper phosphate, Cu 3 (PO 4 )2,
is
insoluble and
is
precipitated, together with basic phosphates, upon the addition of diammonium phosphate to a solution of copper
sulfate.
15. Analytical.
Copper
is
the intense blue color of the
ammonia complex, and by
recognized qualitatively by the
precipitation of the sulfide by hydrogen sulfide in acid solution. Nickel also gives a blue ammonia complex, but its sulfide is not precipitated in acid solution. strip of iron in a not too acid copper solution will be coated with metallic
copper. This is frequently a convenient and delicate test. The detailed methods of separation are indicated in Appendix VI. Copper is often determined quantitatively by
the electrolytic precipitation of the metal in acid solution upon an accurately weighed cathode. This method affords a separation from the baser metals as well. A number of reactions are of importance in quantitative determinations, SI- = 2CuI The liberated iodine is I,-. (a) 2Cu++
+
2
titrated with standardized thiosulfate.
Other oxidizing such as ferric ion must be removed, 2Cuagents (fe) ++ = 7CNH CNO~
(NH 3 )
+ + 2NH + + 6NH
4
2Cu(CN)
solution
3.
The ammonia
is
titrated with
standardized cyanide to the disappearance of the blue color. This method is not as accurate as the iodide reaction.
17]
SUBGROUP
I.
COPPER, SILVER,
2
2
AND GOLD
113,
(c)
2Cu++
4
.
+ 2CNS- + SO + 2H O = 2CuCNS + 4H+

The
precipitate may be ignited and weighed as or titrated with iodate in the presence of concenCii2S, ~ trated hydrochloric acid: 4CuCNS + 7IO 3 + 14H+ 14C1- = 4Cu++ + 4SOr + 7IC1 2 + 4HCN + 5H 2 O.
+ S0
SILVER
16. Occurrence. Native, or free silver is an important source of the element. It is usually alloyed with other of the noble metals. The most important naturally occurring compound is the sulfide, argentite, or silver glance, Ag 2 S. It
sulfide,
frequently occurs in solid solution with copper and lead and as the sulfo-antimonite, Ag 3 SbS 3 and arsenite,
,
and tellurides also occur. Silver chloride, AgCl, called horn silver, is an ore of some importance, and often contains the bromide and iodide in small amounts. The sulfate also occurs, being formed
selenides
AgaAsSs. The
through the oxidation of the sulfide. The average percent8 age of silver in igneous rocks is estimated as 10~ 17. Metallurgy. The recovery of silver from copper ores has been mentioned. Much of the lead smelted from lead sulfide contains silver. This is now recovered by Parke's process, which is essentially an extraction of the silver from the molten lead by means of zinc. Solid zinc is but slightly soluble in lead at temperatures just above the melting point
.
of the latter.
However, silver at these temperatures is about 3,000 times more soluble in the zinc than in the molten lead. Hence zinc in small amounts, usually 0.8 to 1.5 per cent, is stirred with the molten lead, and the greater portion of the silver is extracted. The zinc is removed from
by distillation. The small amount of lead present removed by oxidation and absorption of the lead oxide on a cupel of bone ash. The extraction of silver from comparatively pure silver ore is accomplished either by (1) amalgamation, or (2)
the silver
is
114
REFERENCE
[Ch. VII
leaching processes. The first depends upon the conversion of silver sulfide into chloride by copper chloride, Ag 2 S
+ +
Cu++
2C1~~
= 2AgCl + CuS; and
the decomposition
of the chloride
by mercury, AgCl
silver is recovered
HgCl. The
(amalgam) from the amalgam by dishave been employed.
+ Hg = Ag
tillation of the
mercury.
A
may
number
of leaching processes
sulfide ore
which
is
may be roasted to convert the sulfide into sulfate, may then be extracted with water. Or the sulfide
be roasted with salt to convert it into chloride, which then leached, either with concentrated brine, the solubility being due to the formation of AgCl 2 ~, or with thiosulfate,
forming the complex Ag(S 2 O 3 )2
tions of the alkali cyanides are
now
However, solugenerally employed, as

-
the metal and
all of its
compounds
~
are readily dissolved
by
2
this reagent in the presence of air:
2 2 4Ag(CN) 2 ~ 2 2 2Ag(CN) = Ag(CN) 2~~ + Cl~. The silver is precipitated from the cyanide solution by zinc or aluminum. The more important physical constants 18. The Metal. 2
+ 2H O = + H =
+ 8CN~ + O + 4OH-; Ag S + 4CN~ + O + S + 20H-; AgCl + 2CN~

4Ag
I. Silver is the most lustrous of the metals. In thermal and electrical conductivity it also ranks among the first. It is but little inferior to gold in
have been given in Table

all
malleability and ductility. Silver melted in air always has a blistered surface upon cooling, due to the evolution of
dissolved oxygen during solidification. The solubility of oxygen under 1 atmosphere pressure at the melting point is
20 volumes per volume of the metal.

silver
still
The
cooled solid
contains 0.75 volume of oxygen.

of silver
is
about 9,000 tons. Silver coins are generally 90 per cent silver with 10 per cent copper to increase the hardness. Jewelry usually contains 20 per cent of copper. The electroplating industry consumes a large proportion of the metal produced. The object to be coated is made the cathode in a cell containing a solution
The annual production
19]
SUBGROUP
I.
COPPER, SILVER,
AND GOLD
115
TABLE V
+ K> = Ag O X = 2AgX 2Ag 2Ag + S = Ag S

2Ag
2 2
At 200
with
under
-f-
2Ag 2Ag 2Ag
Ag
SB
2H SO = Ag SO + SO 4- 2H O + 2H+ + 2C1- + *O = 2AgCl + H O + H O + 4CN- + *O - 2Ag(CN)r + 2OH~ Ag+ + e~

-j-
denotes any halogen Also with Se and Te Hot concentrated acid
pressure
See oxidation reduction

table
of
sodium
silver cyanide,
NaAg(CN) 2
as electrolyte.
The
cyanide complex, which gives a very low concentration of silver ion, yields a much firmer deposit than solutions having a higher concentration of the silver ion. Frosted silver ornaments are obtained by roasting the object, made of the ordinary silver-copper alloy, to oxidize the copper on the
surface to the oxide; this is dissolved in sulfuric acid, leaving a layer of pure white silver. Silver mirrors are formed
precipitating the metal from a highly alkaline solution containing the silver ammonia complex ion by the aid of
by
some organic reducing agent, such as glucose or formaldehyde. Approximately 150 tons of silver are used yearly in the production of photographic supplies.
less.
19. Stability of Silver Compounds. Silver ion is colorIt forms such a very large number of slightly soluble
salts
and complexes that
it is
desirable to systematize the
chemistry of these substances by arranging the more important in a list in order of decreasing concentration of silver ion in equilibrium with the solid or complex ion, and a \M concentration of the ion or complex forming molecule. For salts of the types Ag 2 or AgY this is not necessarily the order of the solubility in pure water because the square of the Ag+ concentration enters into the constant for the Ag 2 X. The order is Ag 2 SO 4 AgAc- AgNO 2 Ag 2 CO 3 ,* + AgCl, Ag 2 C 2 4 Ag 2 CrO 4 Ag(NH 3 ) 2 Ag 2 O, Ag(SO 3 ) 2 AgCN, Agl, and Ag 2 S. Any AgCNS, AgBr, Ag(S 2O 3 ) 2
116
REFERENCE
[Ch. VII
substance in the list may be formed at the expense of any substance preceding it. Thus silver iodide may be formed from the chloride: AgCl + I" = Agl + Cl~~. Substances which are close together in the list may be present together in equilibrium at appreciable concentrations of both. Thus
bromide is partially soluble in ammonium hydroxide, and the reaction is easily reversible, depending upon the concentration of ammonia and bromide. The dissociation
silver
constant for the ammonia complex ion + (Ag(NH 3 ) 2 ) = 6 X 10-*.
is,
(Ag + )(NH 4 OH)
The
silver halides are soluble in excess of the halide ion
but they have to form the complex ions AgX 2 ~~, and AgX 3 not been included in the list because of the more complicated equilibria.
potentials of a number of silver complex ions and solids as oxidizing agents are given below. The decrease in
The
oxidizing power is, of course, due to the decrease in concentration of silver ion.
Ag - Ag+ + e- Ag 2SOi + 2e~ 2Ag + SO 4 Ag -J- C H Or - AgC 2 H 3 O2 +<r - Ag 2 C 2 4 + 2e2Ag + C 204 2Ag -f COs~ - Ag 2 CO 8 + 2e- AglOs + <r Ag + IO 8 + Ag + 2NH - Ag(NH 3 ) 2 + e~ + 20H- - Ag 2 + H 2 + 2e2Ag Ag -f Cl- - AgCl + e~ Ag + CNS- = AgCNS + e~ Ag + Br~ - AgBr + e~ Ag + CN- - AgCN +cAg + I- = Agl + e~ Ag -f 2CN- - Ag(CN) + e- A g2 S + 2e~ 2Ag -f- S
2
8
- 0.799 - 0.65 - 0.64

0.47 0.46 0.37 0.37
0.344
-0.222
0.09 0.07 -f 0.04 0.15 0.29
+ + + 0.71
20. Silver Oxide.
The brown
tated
solid
by the addition
hydroxide
is
oxide, Ag 2 O, is precipiof soluble alkalies to silver ion. The
unstable and exists only momentarily.

;
The
oxide decomposes at comparatively low temperatures the partial pressure of oxygen reaches 1 atmosphere at 184 C. However, the rate of decomposition does not be-
22]
SUBGROUP
I.
COPPER, SILVER,
AND GOLD
117
come rapid until the oxide is heated much above this temperature. The decomposition is catalyzed by metallic silver. The oxide is distinctly basic in its reactions. It reacts with as weak an acid as carbonic to form the normal carbonate, Ag 2 CO 3 As indicated above, the oxide is soluble in a large number of reagents with the formation of complex ions. The silver ammonia hydroxide, Ag(NH 3 ) 2 OH, is a soluble
.
strong base.
Upon
highly explosive nitride, probably Ag 3 21. Silver Halides. Silver fluoride
standing, the alkaline solution forms a or Ag 2 NH.
is
extremely soluble
and forms a number of hydrates. The
solubility of the other
halides is very slight, decreasing with increasing molecular weight. Their solubility in various reagents has been indicated above. The solubility in excess halide to form the complexes, such as AgCl 2 ~, requires a fairly high concentration of the halide. The chloride and bromide are not oxidized by nitric acid, but the iodide is. The halides form a number of solid ammoniates, such as AgCl*3NH 3 Silver chloride, however, is not very soluble in liquid ammonia.
.
The photochemical
properties of the halides are discussed

'
under the subject of photography. The chloride and bromide have the so-called 'sodium chloride" arrangement of the ions in the crystal, while the iodide has two forms, one the zinc oxide and the other the zinc sulfide arrangement (Append. V). The fluoride and chloride are colorless, but the bromide is light yellow and the iodide a deeper yellow. Silver chloride may be separated from the bromide by
taking advantage of the difference in solubility in ammonia. A solution containing 32 g. of ammonia and 20 g. of silver nitrate per liter will dissolve the chloride, but not appreciable amounts of the bromide.
Silver cyanide is precipitated by 22. Silver Cyanide. ~ addition of cyanide, and forms the complex ion, Ag(CN) 2 or Ag(CN) 3 with excess of cyanide. The role of the silver cyanide complex ion in metallurgy and silver plating has been discussed. The complex gives the smallest concentra,
118
REFERENCE
[Ch. VI)
sulfide.
any of the silver compounds except the the electropotential given above it is evident that, in the presence of cyanide, silver is a powerful reduc-
tion of silver ion of
From
ing agent. 23. Silver Nitrate.

cially
The
nitrate
is
prepared commersilver.
is
by the action
soluble.
of nitric acid
Its
upon
The
salt is
extremely melting point remarkably low, about 200 C.; cast into sticks it is used in medicine under
the name of lunar caustic. At red heat, it is decomposed into metallic silver, oxygen, nitrogen, and nitrogen oxides. Many organic substances reduce it to finely divided metallic
example, the black stains produced by the action of the salt upon the skin. The salt is important in the preparation of other silver compounds. In dilute solutions it is used as an antiseptic,
solutions as a caustic. It is also used in indelible inks, especially in laundry markings. 24. Silver Sulfide. The sulfide is the least soluble of all the silver salts. It is formed as a black precipitate by hy-
silver, as, for
and
in
more concentrated
even in highly acid solutions. It is more stable toward decomposition upon heating than the oxide. Strong oxidizing agents dissolve it due to the oxidation of the sulfur. It is also somewhat soluble in concentrated In the presence of air the reaction proceeds ion. cyanide through the removal of the sulfide by oxidation to free
drogen
sulfide,
sulfur. Metallic silver dissolves slowly in hydrogen sulfide with the evolution of hydrogen, 2Ag + H 2 S = Ag 2 S + H 2 in accord with the large positive value for the Ag Ag 2 S couple as given above. 26. Other Silver Salts. In addition to those given above, the following slightly soluble compounds may be mentioned: the phosphate, Ag 3 PO4 arsenite, Ag 3 AsO 3 arsenate,
, ;
;
Ag 8AsO 4
.
Cr 2 O7 and upon standing
but moderately soluble, AgN0 in contact with the solution decomposes according to the equation: 2AgNO 2 = Ag + Ag-*- + NO 82,
ferricyanide, Silver nitrite,

;
Ag 3 Fe(CN) 6 and
;
dichromate,
Ag 2 -
is
26]
SUBGROUP
I.
COPPER, SILVER,
is
AND GOLD
'
119
NO.
The
reaction
reversible.
Silver ion also forms
alums, such as AgAl(SO4 ) 2 -12H 2 O. 26. Photography. The silver halides, as well as the show marked changes when exposed to light, escyanide, pecially that of the violet region of the spectrum. There is a change in color; white silver chloride, for example, becomes a deep greyish blue, and is decomposed into silver and the halogen. The primary photochemical process in a crystal lattice, such as silver bromide, composed of silver and bromide ions, appears to be the following:
Ag
The
result
is
Br+
+ +
h* e~
= Br = Ag
a solid solution of silver and atomic halogen which, upon further exposure, decomposes with evolution of the halogen. The halide which has been thus "activated" by light is acted upon much more readily
in the halide,
the unexposed halide. These photochemical reactions are the basis of the ordinary photographic processes. These may be divided into
is
by reducing agents than
the following steps: preparation of the plate or film, exposure, development and fixation of the negative, and preparation of the positive, or print. Dry plates or films are prepared by coating glass or celluloid with a colloidal suspension of silver bromide or The operation must, of course, be chloride in gelatine. carried out in the dark or in faint red light. The size of the particles of the silver halide affects the sensitivity of the
plate to light; hence the suspension is warmed and allowed to "ripen" until the desired size of the grains is
acquired.
is exposed by projecting upon it moan illuminated image. It is then developed by mentarily placing in a bath containing a reducing agent (various phenols, such as pyrogallol, metol, and hydroquinone are usually employed). The rapidity of reduction of the silver
The
plate or film
120
REFERENCE
is
[Ch. VII
halide
upon
it;
and as a
proportional to the intensity of illumination falling result the image on the plate is the "nega-
tive" of the original in that the bright portions are represented by heavy deposits of silver and the dark portions by
faint deposits. The action of the reducing agent is stopped when the proper contrast is obtained, and the plate "fixed" by dissolving out the unreduced silver halide with sodium
thiosulfate solution ("hypo"). The process of printing is essentially the
same as making
the negative, but since the sensitized paper is illuminated through the negative, the image is again reversed, and now appears with the light and dark portions corresponding to the original.
sion in
On
the slower papers silver chloride suspen-
albumen is used, while the faster papers employ The print may be toned by silver bromide in gelatine. treating with solutions of sodium chloraurate, NaAuCl 4 or potassium chlorplatinite, K 2 PtCl 4 which replace the pre,
cipitated silver by gold or by platinum. The former gives a red tone, and the latter dark grey. sepia tone is obtained
by treating the print with collodial sulfur which converts the silver to silver sulfur. Blue tones are given by a treatment with ferric chloride and potassium ferricyanide. The silver reduces the ferric to ferrous which then reacts with
the ferricyanide to give Prussian blue. After It is possible to reverse a negative to a positive. developing a film but before fixing, an acid oxidizing agent
used to oxidize and remove the metallic silver. The film next re-exposed to light to activate the remaining AgBr which was not affected by the initial exposure. The film is then redeveloped and fixed. By this treatment the original dark and light areas of the film are interchanged. "Orthochromatic" and "panchromatic" plates, more sensitive to the red, yellow, and green light, are prepared by adding to the gelatine various dyes, which absorb these longer wave lengths and thus utilize their energy for the activation of the silver halide.
is
is
27]
SUBGROUP
I.
COPPER, SILVER,
AND GOLD
121
In color photography of the coupler type, the primary process is again the reduction of exposed silver bromide
The emulsion, however, contains a comthe coupler, which reacts with the oxidation product pound, of the developer to give a dye. Thus if p-aminodiethylaniline is used as the developer it is oxidized by the silver halide and the product of the oxidation reacts with the
to metallic silver.
The emulsion
coupler (for example, acetoacetic ester) to give a green dye. is coated with at least three layers, each sen-
sitive to a different region of light frequency. By the use of several couplers with various reducing agents the range
of colors
is
covered.
As a
final
step the metallic silver
is
removed, and the dyes give the color image. 27. The + 2 and + 3 Oxidation States. Ozone acts " solutions of Ag4 forming AgO+ and Ag" ", probably upon
"
1
by the following steps: + + 3 =
Ag
AgO+ + + 2H+ = 2Ag++

2
+HO
2
At equilibrium the
is quite large. The solutions are highly unstable as the ions oxidize water Powerful oxidizing agents 2 readily with the evolution of 2 oxide The in alkaline solution form AgO and Ag 2 3
ratio of
Ag++ /AgO+
quite stablfe at ordinary temperatures if kept dry, and is a " convenient source of Ag4 4 since it dissolves readily in cold
is
"
nitric acid.
Peroxydisulfate oxidizes
Ag+
in acid solution:
S2
2Ag+ = 2S0 4
2Ag++
The
2 ion
forms complexes with a coordination number
electrolytic oxidation of a silver nitrate solution in the presence of pyridine forms orange red crystals The difluoride of the complex salt, Ag(C 5 5 N)4(NO 3 )2.
of four.
The
the action of fluorine upon the metal. At its melting point, 690 C., it has about 0.1 atm. pressure of F 2 Approximate values for the standard
AgF 2 may
be
made by
.
potentials are :
122
REFERENCE
[Ch. VII
VOLTS 25
+ H O - AgO+ + 2H+ + e~ 20H- + Ag = 2AgO + H + 2<r 2OH- + 2AgO = Ag O 4- H O + 2e~

Ag++
2
Ag + -Ag++
ca
-1.98
2.1
0.57 0.74
28. Analytical.
Silver
is
detected by the precipitation of
the chloride, insoluble in nitric acid, but soluble in ammonium hydroxide. It may be distinguished from the
slightly soluble lead
and mercurous chlorides by the
fact
that the former
soluble in hot water, but not in ammonia, while the latter turns black with ammonia. Silver is deis
termined gravimetrically by precipitating and weighing a? the chloride, bromide, or as the metal precipitated electrolytically. Silver may be titrated volumetrically with a solution of thiocyanate. Ferric ion is used as an indicator, since the deep red ferric thiocyanate is less stable than the silver salt, and the red color appears only when the silver has been almost completely precipitated. Silver is also titrated in dilute nitric acid with a standardized solution of alkali
chloride or bromide, by taking advantage of the coagulation and settling of the precipitate with sufficient rapidity to permit the observation of any precipitate produced by fur-
ther addition of the halide.
GOLD
29.
Occurrence.
Gold
.
is
found in nature as the free

2,
metal, as the telluride,

lurides, e.g.
AuTe
and
also as
complex
tel-
AuAgTe 4 The
sulfide, selenide, or chloride
do
not occur.
Sea water contains gold to the extent of 0.1 to
0.2 milligram per ton. The name reef gold is given to the deposits of gold occurring in quartz veins. Upon the
weathering of the auriferous rocks, the gold has been washed into sand and gravel beds to form alluvial or placer Native gold nearly always contains silver and deposits.
the platinum metals.
30]
SUBGROUP
I.
COPPER, SILVER,
AND GOLD
123
worked
The richer deposits of gold have been 30. Metallurgy. for centuries by methods which recovered only the
larger particles of the metal and to low grade ores. The crude
which could not be applied methods of placer mining have been the simple agitation or washing of the gravel with water to bring about a separation of the heavy gold particles from the lighter materials. The use of mercury as an aid in the process by the amalgamation of the metal was probably introduced as early as 500 B.C.
The modern metallurgy

silver.
of gold
is
quite similar to that of
Gold in copper and lead ores is recovered, along with the silver, by methods already discussed. The separation of the gold from the silver is known as "parting," and is usually carried out either by electrolytic methods or by the
use of solvents, such as concentrated sulf uric or nitric acids, which dissolve the silver by oxidation, but not the gold. In the former case the impure metal is made the anode, with a
solution of chlorauric acid as electrolyte. Pure gold deposits on the cathode. Silver is precipitated as the chloride toIf gether with the platinum metals in the anode mud. excess silver is present, the electrolyte may be silver nitrate solution, in which case gold remains as sludge at the anode and silver deposited on the cathode. The introduction of the cyanide process by Macarthur and Forest about 1890 has contributed enormously to the
world's gold supply through rendering available for commercial treatment low grade ores and also "tailings" from the amalgam process. The potential of the half reaction,
Au + 2CN- = Au(CN) 2 ~ +
by the oxygen: 4Au + 8CN~ + O 2 + 2H 2 O = 4Au(CN) 2 + 4OH". Hydrogen peroxide appears to be formed as an intermediate step (cf. Ill 4). The reaction is not rapid and requires a number of days. The gold is precipitated from
er, is about + 0.6 volt, that the gold in the presence of cyanide is a good reducing is, agent; hence by treating gold ore with a dilute cyanide solution in the presence of air, the metal is easily oxidized
124
REFERENCE

by
electrolysis.
[Ch. VII
the solution
by
zinc or
after being pulverized in a mill,
may
first
High grade ores, be washed over
amalgamated copper particles which do not
plates to remove the larger gold dissolve rapidly in the cyanide. The
amalgam is scraped off the plates, and the gold recovered by distillation of the mercury. The more important physical properties 31. The Metal.
of
are given in Table I. Gold is the most malleable and ductile all metals. It may be rolled into sheets 0.00001 mm. thick
and drawn into wire which weighs but 0.0005
g.
The world's yearly production is about

used in jewelry
is
1,000 tons.
per meter. The gold

alloys
alloyed with copper.
The copper
than pure gold. The curves for the alloy show a minitemperature-composition mum melting point at 890 C. with a composition of 82 per cent gold. The purity of the metal is usually expressed in carats, that is, the number of parts of gold in 24 parts of the
are redder, harder, and
more
fusible
best jewelry is 15 to 18 carat gold. American 21.6 carat (90 per cent). Gold is deposited in coinage electroplating from a solution of aurocyanide, and much
metal.
The
is
cheap jewelry
is
manufactured by so depositing a very
thin coat of gold on copper.

easily obtained in the colloidal state, especially in the presence of other stabilizing colloids. Thus, purple of
is
Gold
Cassius is finely divided gold adsorbed on a hydrosol of stannic acid. The gold colloids may be formed by reduction of gold solution with chemical agents, or by electrical dispersion, using an arc between gold electrodes under water.
TABLE
2Au
2
8
VI At about 150; with Br '

2
REACTIONS OF METALLIC GOLD
+ 3C1 - 2AuCl Au + 2Te - AuTe 2Au 4- 6H Se0 - Au (SeO + 3SeO + 6H O Au + 5H+ + 4C1- + NOr = HAuCi + NO + 2H - 2Au(CN) - + 2OH2Au + 4CN- + *O + H 2Au + 2Na S - 2NaAuS + Na S 2Au + I* - 2AuI
a 8
also
4) 8
Solution
regia
in
aqua
32]
SUBGROUP
I.
COPPER, SILVER,
AND GOLD
125
32. Equilibria between Oxidation States. Aurous ion unstable in respect to the decomposition: 6Au+ + 3H 2 O = 4Au Au 2O 3 6H+ (about 0.3 volt) hence only those aurous compounds and complexes which are relatively less soluble and less ionized than the corresponding auric comis
pound can be prepared in solution. The only aurous compound which appears to be really stable with respect to the
auric
in
solution
is
the aurocyanide:
+ 2CN- =
VII.
Au(CN) 4
~~
+ 2Au
3Au(CN) 2 -.
Oxidation reduction potentials are summarized in Table The value given for the formation of aurocyanide, 0.6 volt, may be too high, as gold does not appear to dis+ solve in cyanide solution with the evolution of hydrogen.
TABLE
Au = Au +
Au Au
VII
OXIDATION REDUCTION POTENTIALS OF GOLD
+ 2CN- - Au(CN) - + <r AuBr ~ + e~ + 2Br- - ~ = AuBr ~ + 2e~ 2Br~ + AuBr 4C1- = AuClr + 3e~ Au + Au + 4OH- - AuO ~ + 2H O + 3<r
2
Au+ - AU+++
+ e~ + 2*2
ca ca
1.68 1.29
+0.6
ca
0.96 0.82
1.0
0.5
Auric chloride and bromide decompose upon heating to give the aurous halide: AuCl 3 = AuCl + C1 2 Many of the
.
auric
A
all
number
unstable with respect to the reaction, 3Au++ = Au the exception of the sulfide AuS. Like mercuric sulfide this gold sulfide is very slightly soluble and may be precipitated from a solution of auric chloride. 33. Oxides. The aurous oxide, Au2O, is said to be formed by the action of dilute potassium hydroxide upon aurous chloride, but it is very unstable and, in excess hydroxide, gives the metal and aurate, AuO2~. The addition of
compounds, however, decompose, giving the metal. of + 2 compounds also exist, but they are
,
2Au +++ with
hydroxide to auric solutions gives a precipitate of Au(OH)g, or more probably the hydrous sesquioxide, Au 2 O$. This is amphoteric, and is somewhat more acidic than basic. The
126
REFERENCE
[Ch.
VII
alkali aurates,
such as
KAuO
alkaline earths are not.
are soluble; but those of the .The oxide forms with ammonia the
2,
An 3 highly explosive gold "fulminate," probably 2 oxide, AuO, is also known. unstable Fluorine does not attack gold at ordinary 34. Halides. temperatures, but at higher temperatures a slight reaction
.
AuNNH
fluoride is completely hydrolyzed by water, Chlorine attacks gold in the auric hydroxide. forming neighborhood of 150, forming AuCl 3 At somewhat higher temperatures the aurous chloride, AuCl, is formed. This Both chlorides are soluble is but slightly soluble in water.
occurs.
The
in excess hydrochloric acid, forming, respectively, HAuCl 4 and HAuCl 2 The latter is unstable, as discussed above.
.
usually prepared by the action of aqua regia upon gold. Sodium chloraurate, NaAuCl 4 *2H 2 O, is employed in photography in toning prints. The two bro-
Auric chloride
is
mides, AuBr and AuBr 3 are analogous in most respects to the chlorides. Gold is slowly attacked by iodine, forming
,
Aul. However, there appears to be a measurable equilibrium 2Au + 12 = 2 Aul. The aurous iodide is also formed by the
reaction:
Au 2 O 3 + 6HI = 2AuI + 3H 2 O + 2I
2,
or
by the adunstable.
dition of iodide to the auric chloride. Auric iodide

35. Sulfides.
is
Gold and sulfur do not unite when heated but gold is dissolved by molten alkali polysulfides, together, forming thioaurites and possibly some thioaurates. Hydrogen
sulfide in
warm
and unstable sulfide, AuS, appears to be formed. 36. Other Compounds. Mention has been made of the occurrence of gold telluride, and also of the stability and
precipitate of gold
acid solution gives with AuCl 4 a sulfur. In cold solution some of the
"~
importance of the cyanqaurites. The alkali cyanoaurites, such as KAu(CN) 2 are soluble. Auric nitrate and sulfate
,
are so highly hydrolyzed that auric oxide very concentrated solution of these acids.
37. Analytical.
is
soluble only in
The presence
of auric gold
may
be de-
termined by the rose coloration (colloidal gold) produced
37]
SUBGROUP
I.
COPPER, SILVER,
AND GOLD
127
upon the addition of a dilute solution of stannous chloride to the auric solution in excess hydrochloric acid. Gold, in the form of auric chloride, is sometimes determined quanti" 3I~ = Aul I2 tatively by the reaction, AuCl 4 4C1-,
the liberated iodine being titrated with thiosulfate (cf. X 21). Gold ores are usually analyzed by the fire assay. The first step in the assay is the separation of the ganguc,
and the concentration of gold and silver in a lead "button." This operation may be carried out in a shallow clay dish called a "scorifier," in which the sample of ore is heated with a large amount of lead and a little borax. Much of the lead is oxidized, and the oxide forms an easily fusible flux with the silicates and borates. The rest of the lead serves to collect the gold and silver, and when the molten mass is cooled the lead is found as a small lump or button which may be separated from the slag. This process is sometimes carried out in a crucible with a mixture of ore, fluxing agent,
lead oxide, and some reducing agent. The latter reduces some of the lead oxide, and the metal collects the gold and
silver as in the scorification process. The second step is the separation of the gold and silver from the lead. The button
bone ash called a "cupel." The lead oxidizes, and the liquid oxide is readily absorbed by the bone ash, while the liquid gold and silver remain in a small globule. The third step is the "parting" of the gold and silver. The button is flattened by hammering and treated with nitric acid to dissolve out the silver. Unless there is a considerable excess of silver, more must be added before the separation can be accomplished, as otherwise the silver atoms are removed from the surface of the button but the crystal lattice is not destroyed, and the action soon stops.
is
heated in a
little
cup
of
However,
if
there
is
a large excess of
silver,
the crystal
is
completely disintegrated, and the finely divided gold remaining may be fused and weighed. Gold is readily separated from the platinum metals by precipitation with hydroquinone in 1.2N HC1 solutions.
128
REFERENCE
[Ch. VII
In order to of Subgroup I Potentials. the stabilities of the oxidation states of the three compare elements of Subgroup I, the following summary is given for the potentials in acid solution.
38.
Summary
Chapter VIII
.SUBGROUP
II.
AND MERCURY
1.
ZINC,
CADMIUM,
The elements of Subgroup II, zinc, Zn, cadmium, Cd, mercury, Hg (hydrargyrum), differ from the elements of the main group in much the same way that copper, silver, and gold differ from the alkali metals. Thus the subgroup elements are more noble, their hydroxides are less basic, and their ions have a greater tendency to form complex
,nd
These properties depend upon the much higher ionization potentials of the atoms and the smaller size of the resultant ions (Table I). The nfelting points of the elements in
ions.
Subgroup II are much lower than those of the main group. They all form + 2 positive ions, but in addition, mercury f forms an unusual series of compounds of the ion, Hg 2 and cadmium appears to form the + 1 chloride and oxide. These elements are less noble than the corresponding elements of Subgroup I, and their hydroxides are more
" ""
f
acidic.
Zinc and cadmium resemble each other much more closely than they do mercury. They are distinctly electropositive, are readily oxidized by hydrogen ion, and their oxides are reduced with difficulty; while mercury is a noble metal, and
its
oxide
is
easily
decomposed upon simple heating.
The
solubility of the oxide in water increases with increasing size of the metal ion. Zinc oxide is amphoteric, dissolving readily
in
both acids and bases.
Cadmium and
129
mercuric oxides
dissolve in acids,
and unstable cadmates and mercurates are
130
REFERENCE
[Ch. VIII
Both zinc and cadmium form stable hydroxbut mercury does not. Mercuric salts are very highly hydrolyzed, notwithstanding the appreciable solubility of mercuric oxide. One of the outstanding characteristics of the subgroup is the slight dissociation of the chlorides, bromides, and iodides. This property is most pronounced with the mercuric ion. In the most stable salts and complexes, the apparent ionic radii are 10 or 15 per cent less than the values given in Table I, as the high attractive force is able to distort the ions from their normal shapes (cf. VII 2).
also
known.
ides,
*-
TABLE
ATOMIC AND PHYSICAL PROPERTIES OF ZINC, CADMIUM, AND MERCURY
3]
SUBGROUP
II.
ZINC,
CADMIUM, AND MERCURY
131
ZINC
2.
AND CADMIUM
The principal zinc ores are the sulfide, called sphalerite or zinc blende; and the carbonate, ZnS, ZnCO 3 smithsonite. Other ores are: willemite, Zn 2SiO4
Occurrence.
,
;
calamine, Zn 2 (OH) 2 SiO 3 zincite, ZnO; and franklinite, [Fe, Zn, Mn](FeO 2 )2- The average percentage of zinc present in igneous rocks is estimated as 4 X 10~ 5 Most zinc ores contain some cadmium. The average ratio of zinc to cadmium is about 200 to 1. The yellow cadmium sulfide sometimes occurs fairly pure and is known as green.
ockite.
The major portion of the zinc ore is 3. Metallurgy. smelted by reduction with carbon, although more than a hundred thousand tons of pure zinc are now produced yearly by a process which combines the extraction of the ore by leaching, and the electrolytic reduction of the metal from the solution. In the former process the ore is first crushed and concentrated by washing out the lighter rocks, or, in the case of the sulfide, by "flotation" methods (see Metallurgy of Lead). Sulfide and carbonate ores are roasted to convert them into the oxide: 2ZnS + 3O 2 = 2ZnO
2SO 2 Much of the and made into sulfuric

.
sulfur dioxide liberated

acid.
is
recovered
coal,
The
oxide
is
mixed with
and the mixture heated

long).
temperature
in small clay retorts (4 to 5 feet of 1,200 to 1,300 C. is required for
reduction, and as the boiling point of the metal is only 907, the metal is vaporized as soon as it is liberated:
sufficient excess of coal is emto prevent the formation of carbon dioxide, since ployed small condenser is placed zinc is oxidized by the dioxide.
ZnO + C = Zn + CO. A
over the mouth of the retort, and its temperature is controlled so as to condense the metal to the liquid state. If the temperature of the condenser is below the melting point of the zinc, the metal collects in the form of a fine powder called zinc dust, which also contains a small per cent
32
REFERENCE
[Ch. VIII
best conditions, some zinc dust is and 10 per cent or even more of the zinc escapes formed, from the condenser along with the carbon monoxide. The liquid is drawn off and cast into molds, forming what is
oxide.
Even under the
known
iron
as "spelter." It usually contains, as the principal impurities, a per cent or so of lead and smaller amounts of
and cadmium. The metal
may
be purified by
distilla-
or in hydrogen, but it is difficult to effect a separation from the lead. complete In the electrolytic process sulfide ore is first carefully roasted at a low temperature and under these conditions forms largely sulfate. The ore is then leached with dilute
tion in
r
vacuum
sulfuric acid,
and the acid
sulfate solution treated with a
small quantity of zinc dust to precipitate the nobler metals, as these would deposit along with the zinc upon electrolysis of the solution. Although the potential required to
precipitate zinc is 0.762 volt greater than the reversible reduction potential for hydrogen ion, the overvoltage of hydrogen on pure zinc is sufficiently great (1.23 volts in IN + to ) permit the deposition of zinc in acid solution if a high cathodic current density is used. Electrolytic zinc is very pure, and commands a higher price for that reason. The annual production of zinc is over a million tons. Cadmium is both more easily reduced and more volatile than zinc consequently, it is concentrated in the first portions of the distillate in zinc smelting, and may be recovered
from the zinc by fractional distillation. However, most of the commercial product now comes from the electrolytic zinc process, the cadmium being precipitated along with
the more noble metals in the purification of the electrolyte. 4. The Metals. The more important physical properties have been summarized in Table I. Zinc takes a good white metallic luster upon polishing, but the surface quickly tarnishes to the familiar blue-grey tinge. Zinc is hard and brittle at ordinary temperatures, but between 100 and 150 it becomes malleable enough to permit rolling and
4]
SUBGROUP
II.
ZINC,
133
drawing. At somewhat higher temperatures, it becomes so may be pulverized in a mortar. These changes to be due to allotropic forms, but the transitions appear from one form to another have not been definitely determined. Zinc is used in making brass (see Copper) and many other alloys. It is used in dry cells (see Manganese) and the prepabrittle that it
ration of zinc pigments (see Oxide, Sulfate, and Sulfide).
The largest use of the metal, however, is in galvanizing iron. The process is carried out in three different ways: (1) dipping the iron into molten zinc, (2) depositing the zinc upon the iron by electrolytic reduction, (3) exposing the iron to the action of zinc vapor, called "sherardizing." Galvanized iron resists the action of weather better than pure iron, largely due to the impervious coating of basic zinc car-
bonate on the surface, but in part to the fact that the electropositive character of the zinc tends to prevent a hole wearing through the iron by furnishing electrons in place of the iron. Zinc dust is employed as a reducing agent in the manufacture of dyes. Cadmium has a silver white color with a slight bluish tinge. It is not as hard as zinc, and at ordinary temperatures is much more ductile and malleable. Like zinc, however, it becomes very brittle at higher temperatures, the change likewise appearing to be due to a crystalline transition.
less
The
electrical conductivity of
cadmium
is
somewhat
than that of zinc. is used as a substitute for tin in antifriction metals and solders, its principal use being in bearing metals
Cadmium
copper wire adds strength with but small reduction in the conCadmium plating is now used to rust-proof ductivity. wires, tools, and other iron and steel articles. After plating,
the articles are heat-treated, thus alloying the cadmium and iron. Corrosion tests indicate that cadmium plate and zinc plate have about the same resistance.
for automobiles.
Its presence in small
amounts
in
134
REFERENCE
[Ch.
VIH
Reactions of the Metals. Zinc dust is subject to spontaneous combustion in moist air, but in more compact forms does not burn readily until heated above 500 C. Pure zinc is almost insoluble in dilute hydrogen ion, due to the very large overvoltage of the hydrogen. If, however, the metal be touched with some metal with a low overvoltage for hydrogen, such as nickel or platinum, the evolution of hydrogen takes place rapidly on the surface of the other metal, and the zinc dissolves. The high positive value of the
5.
oxidation-reduction potential (Table I) renders it possible The to dissolve zinc by a number of oxidizing agents.
metal
is
soluble in rather concentrated alkali with the
evolution of hydrogen and formation of zincate. These and other reactions are summarized in Table II.
TABLE
2Zn -f Oa - 2ZnO Zn -f 2H + = Zn++ -f H 2 Zn + 2H 2 O - Zn(OH) 2 -f
II
REACTIONS OF ZINC METAL
Upon
heating
Slow with pure zinc With steam at high temperature
Zn -f OH- + H 2 O - HZnO 2 + H 2 ZnS Zn + S Zn -f- X 2 = ZnX 2 Zn = Zn++ -f 2e~ Zn + CO 2 - ZnO + CO 4Zn + 2O 2 -f 3H 2O -f CO 2 = Zn 4 CO 8 (OH)6
With concentrated
alkali
Also with Se, Te, P, As, etc. is any halogen 0.762 volt At red heat
The
protective coating surfaces
on zinc
The
reactions of
cadmium
are, in general, similar to
those
of zinc, but the lower positive value of the oxidation reduction couple, 0.402 volt, renders it considerably less reactive
Tvith oxidizing agents. alkali.
6.
Unlike zinc,
Ions.
it
does not dissolve in

ions
Zinc and
Cadmium
The
Zn++ and Cd" "*

1
are colorless and poisonous to most organisms, cadmium so than zinc. Zinc ion is rather highly hydrolyzed, while cadmium ion is only slightly so. Zinc ion forms as its
more
more important
slightly
,
soluble
4,
8
compounds: Zn(OH)2,
4 )2,
ZnCO.vnZn(OH) 2
ZnNH PO Zn (PO
4
ZnP 2 O ZnC 2O4f

7,
7]
SUBGROUP
,
II.
ZINC,

,
135
Zn(CN) 2 Zn(IO4 ) 2 Zn 2 Fe(CN) 6 and ZnS. Its most stable and HZnO 2 ~. complex ions are ZnCNHs)^" Zn(CN) 4 Cadmium ion forms the precipitates: Cd(OH) CdCO 3 nCd(OH) 2 Cd(CN) 2 Cd 2 Fe(CN) and CdS; and the com+ plex ions, Cd(NH 3 )4+ Cd(CN) 4 ~, and CdI 4 ~.
,
1
",
2,
6,
Oxides and Hydroxides. Zinc oxide, ZnO, occurs as the mineral zincite. It is an important commercial commodity, and is prepared by the oxidation of the metal or directly from the oxidized ores by heating a mixture of carbon and ore in an air blast. The carbon reduces the oxide, but the zinc vapor is immediately reoxidized, and the oxide carried along as a fine dust in the flue gas, from which it is finally recovered by the use of filter bags. This oxide is used extensively as a white pigment, generally mixed with white lead. It is employed in the manufacture of automobile tires, and in medicine as a base for various ointments. It may be formed by gently heating the hydroxide, but it will not combine with water to form the hydroxide. It is yellow when hot, and white when cold. The arrangement of the zinc and oxide ions in the crystal lattice is given in
7.
Appendix V.
The hydroxide is precipitated upon the addition of hydroxide ion to a solution of zinc ion. It is amphoteric, ana
readily soluble in excess hydroxide and in acids:
Zn(OH) 2 = Zn++ Zn(OH) 2 = Zn0 2
+ 2OH~ ~ + 2H+
K K
,
= =
4.5
1
10' 17
.
10~ 29
The
such as are prepared by fusion 2 ZnO 2 of the two oxides, but are highly hydrolyzed in solution. Zinc hydroxide is soluble in ammonium hydroxide, due to the stability of the complex, Zn(NH 3 )4"h4". The value for the = 9.8 X 10"" 10 dissociation constant of the complex is Peroxides in alkaline solution form with zinc salts the hydrated zinc peroxide, ZnO 2 -2H 2 O. The brown cadmium oxide, CdO, is formed by methods
solid zincates,
similar to those discussed for zinc oxide.
Cadmium
hy-
36
REFERENCE
[Ch. VIII
14 droxide, (solubility product, 1.2 X 10~ ), is more soluble and more basic than zinc hydroxide. It does not dissolve
but cadmates are said to be formed by fusing cadmium oxide in potassium hydroxide. Cadmium hydroxide is soluble in ammonium hydroxide, and cyanides with the formation of the complex ions: 7 (K *= 1 Cd(NH 3 )4++ (K = 2.5 X 10~ ), and Cd(CN) 4
in excess hydroxide ion,
"
10~ 17 ).
hydrated cadmium peroxide similar to the

,
zinc peroxide exists, and cadmous hydroxide, Cd 2 (OH) 2 appears to form when a base is added to the unstable
cadmous
agent.
8.
chloride.
The hydroxide
is
a powerful reducing
Halides.
Although zinc and cadmium fluorides are
but moderately soluble, the other halides are readily soluble. They crystallize from their solutions as hydrated salts, usually with 4 moles of water at low temperatures, and one mole at higher temperatures. Solutions of the zinc salts
are distinctly acid by hydrolysis, and readily precipitate basic halides upon the addition of dilute alkali. Concentrated solutions of zinc chloride dissolve zinc oxide and set
to form a cement, ZnOHCl, similar to the magnesia cement. The chloride in the fused state also dissolves metal oxides,
and
is
much
used as a flux in soft soldering.
In their concentrated solutions, the halides appear to be slightly ionized, due to the formation of complex ions. This
property is exhibited somewhat by the zinc salts and markThe latter forms, for example, edly by the cadmium.
CdCdCl 4 and CdCdF4

.
The complex
ion,
CdI 4
is
fairly
stable, the value for the dissociation constant being about 5 X 10-7
chloride, Cd 2 Cl 2 appears to be formed by heatthe dichloride and metal together at about 800. It is ing hydrolyzed by water to Cd 2 (OH) 2
Cadmous
9. Sulfates. The crystallization of an aqueous solution of zinc sulfate at ordinary temperature forms the heptahydrate, ZnSO4 '7H 2 O; and solutions of cadmium sulfate
11]
.SUBGROUP
II.
ZINC,
137
form the hydrate, 3CdSO4 '8H 2 O. number of other hydrates also occur at higher and lower temperatures. These hydrates are very soluble in water. Large quantities of zinc sulfate are used in the preparation of the white pigment,
lithopone,
the
reaction
being:
ZnSO4
BaS = BaSO4
+ ZnS. This pigment does not blacken with hydrogen sulfide, as does white lead, and possesses fair covering power. Cadmium sulfate is employed in the manufacture of "standard cells'* for electrical measurements. These cells have an anode of cadmium amalgam, a cathode of mercurous sulfate in contact with mercury, and an electrolyte
of
cadmium
sulfate solution.
10. Sulfides.
Zinc sulfide
is
the only
common
white
metallic sulfide.
precipitated by to solutions of zinc salts.
sulfide is yellow. Zinc sulfide is the addition of alkali or ammonium sulfides
Cadmium =
drogen ion:
HS~~; but it may be in a solution of acetic acid fairly completely precipitated with sodium acetate added to reduce the hydrogen ion con1
ZnS
H"
Its solubility is increased "" 4
by hy-
Zn"
centration.
The value
for the solubility
product
is
4.5
1.4
X X
10~~
24
.
10~~ 28 ),
Cadmium sulfide is much less and may be precipitated from
soluble
(K =
highly acid solu-
Neither sulfide is soluble in excess of sulfide ion, but both are slightly soluble in high concentrations of ammonium hydroxide, due to the formation of the complex
tions.
ammonia
anide.
is
ions.
Cadmium
sulfide is also soluble in iodide, as
mentioned under the
halides,
Cadmium
sulfide is
but it is not soluble in cyan excellent yellow pigment, but
too expensive for extensive application. 11. Other Salts. The nitrates are readily prepared by dissolving the metals or oxides in nitric acid. Normal zinc
carbonate exists in nature, and

zinc solution with
may be precipitated from sodium bicarbonate, but basic carbonates are precipitated from solution by the alkali carbonates. Cadmium shows less tendency to form basic carbonates than does zinc. Basic zinc phosphate, made from the oxide
138
REFERENCE
[Ch.
Vll x
and phosphoric acid, is important as a cement in dentistry. See also Appendix XIX. The separation of zinc and cadmium 12. Analytical. from other metallic elements is indicated in the standard scheme of analysis (Append. VI). The separation of aluminum from zinc, by the precipitation of aluminum hydroxide with excess
ammonium hydroxide,
carries
down con-
siderable zinc as zinc aluminate, and, for this reason, in detecting small amounts of zinc, it is preferable to precipitate the aluminum as A1C1 3 *6H 2 O, by adding ether and hy-
drogen chloride gas. The insolubility of cadmium sulfide in excess sulfide ion distinguishes it from arsenic, antimony, and tin and its solubility in hot nitric acid gives a separation from mercuric sulfide. The precipitation of cadmium
;
sulfide in the presence of cyanide ions serves to distinguish
cadmium from
Zinc
copper. be determined quantitatively by precipitating as the sulfide, igniting, and weighing as the oxide by precipitation as ZnNH 4 PO 4 and weighing as Zn 2 P2O7*, or by precipitation by cathodic reduction from an acetic acidacetate buffer solution. In the electrolytic determination, it is difficult to obtain a complete precipitation of the metal. The most satisfactory volumetric method is the titration of zinc with ferrocyanide. The formation of a brown color with an uranyl solution as an outside indicator is used to
may
determine the end-point, or a few drops of ferrous ion may be added to the zinc solution, in which case the color changes from light blue to pea-green at the end-point. This latter color change appears to be due to the presence of a trace of ferricyanide, which gives a blue color until an excess
of ferrocyanide
is
obtained.
Cadmium may be determined gravimetrically by precipitating as carbonate and weighing as oxide or, similarly to zinc, precipitating as phosphate and weighing as Cd2P2O/. It is impossible to precipitate the sulfide pure enough to
;
weigh as such, as
it
forms complexes,
e.g.,
Cd 2 Cl2S. Cad-
15]
SUBGROUP
II.
ZINC,
139
mium may
also be determined elect rolytically by reduction from a solution of the cyanide complex.
MERCURY
13.
Occurrence.
of gold
Mercury occurs native and

silver,
in
amalalso
gams
HgS.
and
but the principal ore

tellurides,
is
cinnabar,
Complex
selenides,
and chlorides
occur, but they are of slight economic importance. The average percentage of mercury in the igneous rocks is
estimated as 10~ 7
14.
Metallurgy. The extraction of mercury from the sulfide ore is comparatively simple, since the sulfide may readily be converted into the volatile metal, either by roasting in air: HgS + O% = Hg + SO 2 or by roasting with
;
lime:
4HgS + 4CaO = 3CaS + CaSO 4 + 4Hg. The mer-
cury vapor is more easily condensed from the furnace gases than is zinc, because of the greater weight of the molecules of vapor, and also because the vapor is not readily reoxidized by air. The metal is filtered through chamois skin and purified by washing with nitric acid, or mercurous nitrate solution; or by distillation in the presence of oxygen, or other oxidizing agents, which will remove the base metals,
and cadmium. The more important physical properties have been given in Table I. The metal is a silverywhite liquid with a vapor pressure of 0.001 mm. at 20 and 0.28 mm. at 100. Its boiling point is 356.90. A, table of
especially zinc
15.
The Metal.
is given in Appendix IX. The vapor and does not conduct electricity in the cold, monatomic, but if an arc is once struck it conducts readily with the emission of the characteristic mercury spectrum which is very rich in green and ultra-violet light. This mercury vapor arc is much used as a current rectifier, and as a source
densities of the liquid

is
of ultra-violet light for the treatment of certain diseases. The cubical coefficient of expansion of mercury between
140
REFERENCE
is
[Ch. VIII
represented by the expression: a = 1.8006 X 10~ + 2 X 10~8/. Due to this rather uniform expansion and to the fact that the pure liquid does not "wet" glass, mercury is extensively used in thermometers. Its low vapor pressure and high density makes it useful in barometers.
and 300
4
With the exception of iron and platinum, metals readily dissolve in, or are wet by mercury to form amalgams; many of these have been mentioned in connection with other
metals, e.g. sodium, aluminum, gold, and silver. An amalgam of thallium (8.5 per cent Tl) has a very low melting
60 C. be used in thermometers down to Amalgams of tin, silver, gold, and other metals are employed in dentistry. Many attempts have been made to use mercury in heat engines, as the higher boiling point oilers a very substantial increase in the theoretical efficiency over the steam engine, and two plants are now in operation in the United States. These installations employ 300,000 pounds
point and
may
of mercury.
TABLE
2Hg
2
III
+ O - 2HgO Slowly around 350 X any halogen + Xj = HgX-j + S = HgS Upon subliming together 3Hg + 2N0 - + 8H+ = 3Hg++ + 2NO + 4H O Excess acid 6Hg + 2NO + 8H+ - 3Hg ++ + 2ND + 4H O Excess mercury Hot concentrated acid Hg + SQr- + 4H+ = Hg+ + + SO + 2H
Hg Hg
is
8
8 2
16. Equilibria
between Oxidation
States.
The mercu-
rous ion is stable in respect to the decomposition into mercuric ion and mercury: i.e., mercuric ion is reduced by "" 1 + Hg = Hg 2 f f However, the value for mercury: Kg" the potential of the reaction corresponds to an equilibrium " " concentration of Hg 2 H at 25 C., only 166 times that of Hg4 "; hence the equilibrium is easily reversed in case the mercuric compound is much less soluble than the mer"
"
""
curous:
e.g.,
Hg 2S = HgS + Hg and Hg O = HgO +

2
Hg.
Due
to the insolubility of the basic

all
(Par. 26),
ammonia mercuric salts mercurous compounds are decomoosed by
17]
SUBGROUP
II.
ZINC,
141
equation: 2HgSO4 = Hg 2 SO4 + SO 2 + O 2 The couple Hg ++ -Hg + is a stronger oxidizing couple than Hg++ -Hg (Table IV) hence reducing agents first reduce mercuric ion to mercurous. Since the potential of the
.
;
ammonia. The equilibrium lies in the direction of the mercuric form at higher temperatures. In this respect the higher oxidation state is different from copper, since cupric oxide upon heating gives cuprous oxide and oxygen, while mercuric oxide gives mercury and oxygen. Mercuric sulfate, however, decomposes at high temperatures according to the
+ couple Hg -Hg is almost as large, most reducing agents capable of reducing mercuric ion will, in excess, reduce the mercurous ion to mercury as a second step: e.g., 2Hg ++
Sn++ = 2Hg+ + Sn++++, and 2Hg+ + Sn++ = 2Hg " Sn + H+ It also follows from the potential values that fairly powerful oxidizing agents, e.g., bromine water and hot nitric acid, are required to oxidize mercurous compounds
+ +
"
much
to mercuric, unless, of course, the mercuric less soluble or less ionized.
compound
is
TABLE
IV
OXIDATION- REDUCTION POTENTIALS OF
MERCURY
VOLTSM*
+ S = HgS + 2er + 4CN- = H[g(CN) + 2e~ + 41- - HgI + 2c~ + 2e~ 2Hg + 21- - Hg Hg + 20H- = HgO + H + 2e~ 2Hg + 2Br~ = Hg Br + 2e~ 2Hg + 2SCN- = Hg (SCN) + 2er 2Hg + 2C1- = Hg Cl + 2e~ 2Hg + COr- - Hg CO + 2e~ - Hg C C,04 + 2er 2Hg = Hg S0 + 2e2Hg + SO 2Hg - Hg ++ + 2er Hg = Hg ++ + 2tr ++
Hg Hg Hg
4 4
2I 2
+ 0.70 + 0.37 + 0.04 + 0.04
-j-
- 0.098 - 0.14 - 0.22 - 0.2675 - 0.32 - 0.41 - 0.615 - 0.789
Hg a
HgS - S
- 2Hg ++
-f 2e~ Hg++ 4- 2e-
- 0.854 - 0.920
1.05
MERCUROUS COMPOUNDS
17.
solubility of its salts,
Mercurous ion is strikingly similar to silver ion in the and in the potential of reduction to the
142
REFERENCE
[Ch. V.;
metal. However, the mercurous ion is peculiar in. that it is associated into the double ion, Hg 2 ++, not only in solution,
but
it is
in its
compounds in the solid and gaseous state. Indeed somewhat doubtful if the undissociated ion Hg + exists.
the standpoint of atomic structure, the mercurous quite unusual. The variations in the oxidation states of the Subgroup I elements arises through the possibility of removing electrons from the kernel, but the mercurous
ion
is
From
ion consists of the kernel plus one valence electron. Many examples may be given of the association of molecules containing an
:
odd number
of electrons;
and the formation
of
of
may be (Hg Hg) "odd" molecules.
4"*"
correlated with this general behavior The mercurous ion does not form
iodide, or thio-
complex ions with the ammonia, cyanide,

sulfate, as does silver ion.
18.
Mercurous oxide, Hg 2 O, is formed by the action of upon soluble mercurous salts. It is not soluble in excess hydroxide ion. The oxide decomposes rapidly into mercury and mercuric oxide. X-ray patterns of a fresh precipitate show only HgO and Hg. 19. Mercurous chloride, Hg 2 Cl 2 or calomel, is the most important mercurous salt. It is usually prepared by subliming a mixture of mercuric chloride and mercury: HgCl 2 + Hg = Hg 2 Cl 2 It is formed as a white precipitate by the
alkalies
,
addition of chloride to a solution of mercurous nitrate. Mercurous chloride sublimes without melting, and if dry,
Cl 2 molecules, but moisture catalyzes its decomposition into mercury and mercuric chloride. Light causes a partial decomposition of the salt at room
the vapor consists of
Hg
temperature. Mercurous chloride turns dark when treated with ammonia, due to the formation of finely divided mercury and the ammono-basic mercuric chloride (Par. 25). The use of calomel in medicine depends upon its stimulating
action
upon the
liver
and other secretive organs.
The
2e~
is
potential of the reaction:
2Hg
2C1~ = Hg 2 Cl 2
0.2675 volt
(i.e.,
molal chloride ion activity and referred
22]
SUBGROUP
II.
ZINC,
143
to the potential of hydrogen arbitrarily chosen as zero) and the electrode: mercury solid mercurous chloride chloride ion, is often employed as a reference electrode in
potential measurements.
The potential of the electrode changes slightly in air. Thus with 1M KC1 the values are 0.2812 in absence of air. Much work 0.2825 in air and
has been done on the absolute value of this electrode potential, and the value 0.56 volt is usually accepted; the mercury is positive with respect to the solution. 20. Mercurous fluoride, bromide, and iodide resemble
the corresponding silver salts in respect to solubility in water. The iodide is unstable, especially with excess iodide, and decomposes into mercury and mercuric iodide.
21.
Mercurous
sulfide
may
be formed momentarily by
the action of hydrogen sulfide upon mercurous salts, but it immediately decomposes into mercury and mercuric sulfide. Mercurous nitrate and sulfate may be prepared by the
action of nitric acid and of hot concentrated sulfuric acid, respectively, upon excess mercury. The nitrate is readily Both are hysoluble, but the sulfate only sparingly so.
drolyzed, and unless excess acid is present, form slightly soluble basic salts, such as Hg 2 (OH)NO 3 and Hg 2 OHg 2 SO 4 2 0.
Mercurous phosphate,
nitrite,
chromate, bromate, and
iodate, are but slightly soluble. Alkali carbonates precipitate mercurous carbonate from soluble mercurous salts.
The carbonate
is
unstable
.
if
warmed
slightly:
is
= Hg + HgO + CO 2
22.
Hg COs
2
Mercurous cyanide
not stable.
MERCURIC COMPOUNDS
Mercuric oxide, HgO, is slowly formed as a red powder when mercury is heated in air just below its boiling point. It is usually prepared by heating the nitrate or a mixture of the nitrate and mercury: Hg(NO 8 )2 + Hg = 2HgO + 2NO2. The partial pressure of oxygen over mercuric oxide is 9S5 mm. at 500 C. The oxide precipitates
144
REFERENCE

.of
[Ch. VFII
upon the addition of a strong base to a solution

curic salt.
a mer-
from hot seems to be merely a question of the state of subdivision of the solid, as the two forms appear to have the same crystal structure and very nearly the same energy content. The yellow is the more reactive and also the more finely divided. The hydroxide is unstable, but a hydrate, HgO3H 2 O, exists. The oxide is soluble in excess iodide due to the formation of the
Precipitated in the cold, the color is yellow, but solutions, the color is red. The difference in color
complex iodide:
HgO +
2
4I~"
+HO =
2
Hgl 4
due to
2 ~.
+ 2OH~. Its solubility increases slightly weak acidic properties and the formation
HgO + OH~ = HHgO
in alkali,
of
HHgO
10~5
Mercuric ion in solution is more highly hydrolyzed than is to be expected from the value for the solubility of the oxide, Table I. However, the value for the oxide electrode: Hg
Mercuric chloride, HgCl 2 "bichloride of mercury M or "corrosive sublimate/' may be made by heating mercury in an atmosphere of chlorine. The reaction is accompanied
23.
,
- 0.098 volt, indicates + in the solution is that the concentration of Hg+ very small.
+ 2OH- = HgO + H O +
2
2e~,
It is usually prepared, however, by a mixture of mercuric sulfate and common salt. subliming The chloride is moderately soluble in water, and the solubility is increased by excess chloride ion due to the formation
by green
radiation.
The salt in solution is complex ions, probably HgCl 4 but slightly ionized, even less than cadmium chloride, as is indicated by its low electrical conductivity, and by the value of the chloride as an oxidizing agent: Hg 2 Cl 2 + 2C1~~ = 2HgCl 2 + 2e~, -0.53 volt. This value is 0.3 volt lower than the Hg2 ++ -Hg++ couple in spite of the small solubility of the mercurous chloride. The solution is only slightly but the addition of dilute alkali results in the hydrolyzed, formation of various basic chlorides, such as HgCl 2 -HgO. The chloride is much used as an antiseptic and is highly
of
.
25]
SUBGROUP
II.
ZINC,
145
poisonous. It forms a slightly soluble
compound with
albu-
men, and advantage is taken of this fact in administering egg white as an antidote. As a poison it acts partly through the destruction of kidney cells to such an extent that death results in about two weeks from the inability of the body to eliminate its waste products. The commercial preparation is usually mixed with sodium chloride to increase the rate
of solution.
Mercuric fluoride is more soluble and much more hyThe bromide is sparingly 9rolyzed than the chloride. and the iodide still less soluble. The iodide exists soluble, in two modifications, a scarlet form stable below 128, and a yellow form stable above that temperature. The yellow iodide may be super-cooled below the transition temperature, but readily changes to the scarlet when touched. Mercuric iodide dissolves in excess iodide forming the
24.
A solution of the very stable complex iodide, HgI 4 iodide is known as Nessler's reagent, potassium complex and is used in detecting small amounts of ammonia (see
.
below).
25.
Mercuric ammonia compounds
exist in interesting
giving Hg(NH3) 4 4 high (12N) concentrations of such as HgCl2'2NH 3 crystallization,
variety, divisible into four types: (1) Soluble +4". This ion is stable the ion
complexes only at very
NH OH
;
(2)
with ammonia of
ammonia system,
tive ions of
that
is,
ammonia,
NH
(3) basic salts of the are formed from the negathey and similar to 2 ~,
NH
the simplest being of negative ions of water OH~ and O the type HgNH 2 Cl; (4) salts which are both arrtmonolyzed and hydrolyzed. Many complex salts of this latter type exist. The most important are derivatives of Millon's base, OHHgNHHgOH, or Hg 2 NOH'H 2 O. The addition of ammonium hydroxide to mercuric chloride solution precipitates the ammonobasic chloride, HgNH 2 Cl. With mercurous chloride, the same compound mixed with mercury is formed. The ammonobasic chloride is soluble in hydrochlo,
146
REFERENCE
acid
[Ch. VIII
ric
is
and dissolves more readily if some ammonium ion present. Ammonia and mercuric nitrate solution form Hg 2 N'NC>3 and a number of other complex salts. Nessler's reagent (Par. 24) gives, with ammonia, a yellow precipitate,
the iodide of Millon's base,
26.
Hg 2 NI*H 2O.
Mercuric Sulfide. Crystalline mercuric sulfide is both as found in nature, cinnabar, and as prepared by red, subliming together mercury and sulfur; but the sulfide precipitated from solution by hydrogen sulfide is black and amorphous. The black form is transformed slowly into the red by digestion with sodium sulfide. Mercuric sulfide is the least soluble (K = 3 X 10-53 ) of all the metal sulfides, and does not dissolve in hydrochloric or nitric acids. It is, however, soluble in aqua regia and in bromine water, due
to the stability of the complex halides. Hot concentrated nitric acid converts it into the difficultly soluble white complex,
erties,
Hg(NO
and
is
)2*2HgS.
The
sulfide
has weak acidic prop-
somewhat
soluble in a solution of an alkali sul-
but not in ammonium sulfide. The red sulfide is used as a pigment under the name of vermilion. 27. Mercuric nitrate and sulf ate are formed by the action of excess nitric and hot concentrated sulf uric acids upon the metal. Both are soluble, but are rather highly hydrolyzed, and precipitate as basic salts, such as Hg(NO 3 ) 2 'HgO and HgSO4 *2HgO, unless excess acid is present. Normal mercuric carbonate does not exist, but basic carbonates, such as HgCO 3 '2HgO, may be precipitated. Mercuric cyanide, Hg(CN) 2 is soluble, but is even less ionized than the halides, and like them forms a complex ion, Hg(CN) 4
fide
,
When
heated, mercury and cyanogen: = Hg + C 2 N 2 This complex gives the smallest Hg(CN) 2 concentration of mercuric ion of any of the mercuric compounds except the sulfides. Mercuric fulminate, Hg(CNO) 2 is formed by the addition of alcohol to a hot solution of mercury in nitric acid. The dry precipitate explodes upon being struck, and is used
It
decomposes into
.
128]
SUBGROUP
in
is
II.
ZINC,
147
extensively
Hg(CNS) 2
prepared from
Mercuric thiocyanate, percussion caps. " Pharaoh's serpents" are slightly soluble. this salt by making it into a paste with gum-
water. When dried and ignited it burns and forms a voluminous ash which assumes serpentine forms. 28. Analytical. Mercurous ion, like silver, gives a curdy, white precipitate with chloride but, unlike silver chloride, the precipitate blackens with ammonia (Par. 26). The insolubility of mercuric sulfide in nitric acid and in ammonium polysulfide serves to identify mercuric ion. The addition of stannous chloride to mercuric ion in small amounts gives a white precipitate of mercurous chloride, and in excess, a grey precipitate of mercury. With mercurous ion, stannous chloride in small amounts gives an immediate precipitate of mercury. A copper wire in either mercurous or mercuric solutions becomes coated with a grey or silvery deposit of
mercury.
Mercury may be precipitated and weighed quantitatively as the sulfide, or electrolytically as the metal on a platinum cathode. It is sometimes determined by heating the sample
in a combustion tube and passing the vapors through a weighing tube containing gold leaf to absorb the mercury. Mercurous salts may be precipitated and weighed as the chloride. Mercuric salts are sometimes analyzed volumetrically by titration with iodide.
Chapter IX
SUBGROUP
1.
III.
AND THALLIUM
The elements
of
GALLIUM, INDIUM,
III are extremely rare
Subgroup
and
in
of slight industrial importance. of thallium,
They form compounds
which they have an oxidation state of
3,
compounds also of the + 1 the higher positive charge on their ions, they GO not show as great tendencies to form "coordination compounds" or complexes as do the elements of Subgroup II. The first electron is rather easily removed, and as a consequence, compounds of the elements give characteristic colors in hot Bunsen flames; in fact, all of the elements of this group were discovered (between 1860-1875) through spectroscopic
means. The name thallium (from Latin thallus, a budding twig) refers to its green spectrum; and the name indium, to its indigo-blue spectral lines. Gallium was named in honor of France (Latin, Gallia).
and, in the case state. In spite of
The
compounds
are similar to those of
aluminum;
with the exception that the acid character of the hydroxides decreases with increasing size of the atoms, and the potential of the ions as oxidizing agents increases.
2. Occurrence. The elements occur widely distributed, but only in minute quantities. The average percentages of the elements present in igneous rocks are given as: gallium, 10~ u indium, 10" 11 and thallium, 10~ 10 Gallium is a com;
;
constituent of zinc, iron, aluminum, and chromium ores, but is seldom present in quantities as high as 0.01 per
148
mon
3]
SUBGROUP
III.
GALLIUM, INDIUM, THALLIUM
149
cent.
In small amounts, it is a very common impurity in pig iron and in commercial aluminum. Indium is usually associated with zinc blende, and often with ores of lead and tin. Its principal source is zinc ores, in which it sometimes occurs to the extent of 0.1 per cent. It is estimated that
several thousand tons of gallium and indium could be recovered yearly as by-products of the zinc and coal indusThallium is associated with the alkalies, and also tries. with iron, zinc, lead, tellurium, and other elements. It is most commonly obtained from the flue dust of sulfuric acid works in which thalliferous pyrites are burned. The extraction of the metals 3. Preparation of Metals. is largely a problem of separating the small quantities of their compounds from other metallic constituents, and is, therefore, best considered after a discussion of the properties of the various ions. The metals are easily obtained by reduction with zinc, or by electrolysis.
TABLE
50
REFERENCE
[Ch.
IX
of the properties of the metals Table I. Gallium is a hard, brittle, grey metal. It melts just above room temperature, and remains a silver white liquid of low vapor pressure through a temperature range of about 1,500 degrees. The metal expands upon changing from liquid to solid. The liquid supercools readily and may be kept in the liquid state even
4.
The Metals.
Many
in
have been summarized
at
C.
A possible application is in the construction of high
temperature thermometers using quartz tubes. Indium is a lustrous silver metal almost as soft as lead, and is both It is now available in commercial ductile and malleable. quantities. As a coating for bearings it improves corrosion
resistance
oil
film.
and permits the surface to retain a more complete Thallium is bluish-white in color, easily cut
with a knife, malleable, but of low tensile strength. The metal exists in two crystalline modifications with a transition at 226 C. Like the other two metals, the liquid is stable over a very long range of temperature. 6. Reactions of the Metals. Gallium is only superficially oxidized in air at red heat; indium is not appreciably oxidized in air at 25, but burns with a blue flame when heated, forming In 2 O 3 thallium oxidizes slowly at 25, and rapidly at higher temperatures, forming both T1 2 O and T1 2 O 3 Gallium and indium dissolve fairly readily in hydrogen ion with the evolution of hydrogen gas and the formation of the ions; thallium dissolves forming thallous ion or thallous salts. They unite directly with the more electronegative elements, and are, of course, oxidized by even moderately
; .
strong oxidizing agents, as indicated by their oxidationreduction potentials (Table I).

6.
Gallic Ion
its salts
and
Its
Compounds.
Gallic ion
is
colorless
and
with colorless negative ions are white. Gallic oxide, Ga 2 O 3 resembles aluminum oxide. Callous oxide, Ga 2 O, is known but it is unstable with respect to its decomposition into the + 3 oxide and the metal. The hydroxide, Ga(OH)jj, is precipitated by alkali and ammonium
,
7]
SUBGROUP
III.
151
TABLE
II
REACTIONS OF THE METALS
4M 2M 2M 2M
2M
+ 3O - 2M O + 6H+ = 2M+++ + 3H ~ + 2OH- + 2H O = 2MO + 3H + 3X = 2MX

2
2
3
Ga
2
slowly.
With Ga and With Ga
Tl also forms T1 2 O In. Tl forms Tl+ Tl also forma

Se, Te, P,
4-
3S
M Sa
2
TIX
As.
denotes halogens.
Analogous reactions with
hydroxides, and the precipitate
is
soluble in excess of the
reagent, forming gallates. Approximate values for the basic and acidic dissociation constants are:
Ga(OH) 3 = Ga+++
3 3
2
H GaO = H GaO 3-
+ 3OH~
+ H+
K K
= =
5
1
X X
10~37 lO" 16
aluminum, in the presence of carbonate ion, completely hydrolyzed, leading to the precipitation of the hydroxide. The sulfates, nitrates, and halides are soluble, but the solutions are highly hydrolyzed and precipitate
Gallic ion, like
is
upon boiling. A dichloride, GaCl 2 appears to be formed by heating the trichloride with excess of the metal. The salt evolves hydrogen in water and forms basic gallic chloride. Gallic ion readily forms alums. The ferrocyanide is insoluble, even in solutions strongly acid with hydrobasic salts
,
chloric acid.
except or arsenic, and then only

slightly acid.
7.
The white sulfide, Ga 2 S 3 is not precipitated in the presence of other sulfides, such as zinc, copper,
,
when
the solution
is
alkaline or but
aluminum
Gallium is precipitated with the iron Analytical. zinc group in qualitative analysis. It may be
separated from the other elements of the group, except ferric iron, by converting to the chloride and extracting with an ether-hydrogen chloride solution. The iron may be removed by reduction to ferrous and repeating the ether separation. The commercial separation from the zinc, with which it is usually associated, may be effected by converting
152
REFERENCE

and
fractional precipitation
[Ch. IX
into the chlorides,
by sodium
carbonate.
It is
The gallium concentrates in the first precipitate. separated from indium by taking advantage of the
greater solubility of gallium hydroxide in excess alkali. The separation from zinc and indium may also be accomplished
by
fractional electrolytic precipitation.

is
Quantita-
aqua ammonia, removing the excess ammonia by boiling, and is weighed as the
tively gallium
precipitated with
sesquioxide. 8. Indie Ion
and Compounds.
The
+ ion, In
"
"f
,
is
color-
or alkali hydroxides precipitate it as the less; hydroxide 9 In(OH)3. The hydroxide forms the sesquioxide, In 2 O 3 upon heating, and upon strong ignition the oxide, Heated to 300 in hydrogen, the oxide, In 2 O 2 apIn 3 O 4 to be formed. The hydroxide is soluble to a very pears
,
. ,
ammonia
small extent in strong alkali hydroxide (but not in dilute ammonium hydroxide), probably forming indate ion, InO 2 ~. The carbonate is but slightly soluble, and, unlike gallium, is but slightly hydrolyzed. It is soluble in excess ammonium
carbonate, but not in excess sodium carbonate. The nitrate, The halides resulfate, alums, and halides are soluble. semble the cadmium compounds in that they are weak salts.
Mono- and
dihalides are formed
by heating the
trichlorides
with excess metal, but these lower halides are unstable in water solutions: 3In+ = In+++ + 2In, and 3In++ = 2In+++ + In. From analogy to mercurous ion the + 2 ion should have the formula In 2 4 Yellow indium sulfide, In 2 S 3 is
""
1
precipitated by hydrogen sulfide in the presence of very dilute acid. It is somewhat soluble in a very high concen-
The cyanide is but slightly soluble in but dissolves in excess cyanide. The ferrocyanide water, and chromate are also but slightly soluble. 9. Analytical. The separation of indium from indiferous the principal source of the element, is usually accomzinc, plished by dissolving the metal in acid, and precipitating indium and iron by the addition of ammonium hydroxide.
tration of sulfide ion.
11]
SUBGROUP
III.
153
The indium
is separated from the iron present by dissolving the hydroxides and precipitating indium sulfide in acetic acid solution by hydrogen sulfide. In the systematic qualitative separation, indium, like gallium, is precipitated with the iron-aluminum-zinc group.
zirconium and titanium in that the hydroxide not dissolved when boiled with NaOH and Na 2 O 2 but differs in the precipitation of the sulfide from a fluoride
It is similar to
is
,
solution
by
NH OH and (NH
4
1
4 ) 2 S.
10. Equilibria
between Thallous and Thallic

.
Ions.
Thallic ion, Tl^" "*", is a strong oxidizing agent (Table III), + Further reduction rebeing reduced to thallous ion, Tl
4 quires a fairly powerful reducing agent. The reaction, Tl 2T1 = 3T1+, takes place practically to completion. Hot
1
"1" "
water
is
2H +
"*"*" + H 2O = T1+ decomposed by thallic ion: Tl" + |O 2 Thallic compounds decompose in general,
1
heating, with the formation of the thallous compound : T1C1 3 = T1C1 C1 2 and T1 2 S 3 = T1 2 S 2S. e.g.
upon
TABLE
I- = Til e~ Tl Br- - TIBr e~ Tl Tl Cl- = TICi +e~ er Tl - Tl 4 2e~ T1+ - T1+++
III
OXIDATION-REDUCTION POTENTIALS OF THALLIUM

VOLTS
0.77 0.66 0.56 0.336
+ + +
-1.2
Thallous Ion and Compounds. In the solubilities of most of its salts, thallous ion resembles plumbous ion; while in size and other physical properties, basic nature of
11.
it
the hydroxide, and lack of tendency to form complex ions, resembles potassium. Thallous ion is like stannous and plumbous ions in having a pair of valence electrons left in the valence energy level. Thallous oxide, T1 2 O, readily
is fairly
absorbs water to form thallous hydroxide, T1OH. The latter soluble and is a strong base. The decomposition = pressure of steam over the hydroxide, 2T1OH
154
REFERENCE
ICh.
IX
O, reaches one atmosphere at 139 C. The chloride, bromide, and iodide are but sparingly soluble, and the solubility is decreased by the presence of excess halide ion.
2
+H
However, the cyanide appears to be soluble in excess cyanide ion. Thallous sulfide, T1 2 S, is precipitated in neutral or alkaline solution. The solubility product of the sulfide is 24 Thallous carbonate is fairly soluble. given as 1.2 X 10"
.
The chromate, normal phosphate,
chloroplatinate,
and co-
baltinitrite are sparingly soluble. Thallous sulfate is sometimes used in the preparation of poison grain to kill rodents.
12. Thallic
Ion and
Its
Compounds.
Thallic ion resem-
bles aluminum ion except that it is larger, and its hydroxide does not possess acid properties. The hydroxide is extremely insoluble and the soluble thallic compounds such as sulfate and nitrate are highly hydrolyzed. Oxygen reacts with thallium just below red heat to form thallic oxide, T1 2 O 3 at higher temperatures mixed thallic and thallous oxides are formed. Chlorine, passed into a suspension of
;
thallous chloride, produces thallic chloride. Upon evaporation, the hydrate, T1C1 3 -3H 2 O, may be obtained, and in
the presence of
separates.
chloride,
ammonia
The
trichloride forms
the ammoniate, T1C1 3 -3NH 3 complex ions with excess

,
T1T1C1 4
T1 2 S 3
and a complex thallous chlorthallate exists, The bromide is quite similar to the chloride, but
probably thallous triiodide. The sulfide, very unstable, and forms thallous sulfide and
,
the iodide, T1I 3

,
is
is
sulfur.
13. Analytical.
and
its solubility is
Thallous chloride is soluble in hot water not increased in ammonia. It thus
resembles lead chloride. The iodide is much less soluble than the chloride and is considered the most satisfactory test for thallous ion. It is but slightly soluble in thiosulfate. The extraction of thallium from the flue dust of sulfuric acid plants is based upon the slight solubility of the chloride, the non-precipitation of thallous carbonate by alkali carbonates, the precipitation of thallous sulfide by ammonium
13]
SUBGROUP
III.
155
sulfide,
and the reduction of the compounds to the metal
Quantitatively, thallium is usually precipitated by and weighed as the thallous iodide. It may also be determined by titrating with standard permanganate, which
zinc.
in acid solution oxidizes thallous salts to thallic.

14. Potential
Diagram Summary.
ca 0.45
Ga 2+ 4
0.52
ca 0.65
Ga+
0.3363
T1+ 1
----1.247
0.719
T1+ 3
I
Chapter
THE HALOGENS: FLUORINE, CHLORINE, BROMINE, IODINE, ASTATINE

VII.
1.
GROUP
The elements
bromine, Br, iodine,
word meaning
fluorine, F, chlorine, Cl, are called the halogens from a Greek salt-producing, since they all combine with
I,
of
Group VII,
the alkali metals to produce salts like sodium chloride. Element number 85, the heaviest member of the group, is known only in minute amounts as highly radioactive isotopes produced by nuclear reactions. It has been named
astatine, stable/'
symbol At, from a Greek word meaning 'unVery little is known of its physical and chemical
'
Since it is still impossible to discuss the properties. chemistry of astatine in relation to the other elements of the group in any detail, it will be treated separately at the
this chapter. Fluorine and chlorine are gases; bromine is a volatile liquid; and iodine is a solid, easily melted and vaporized. The chemical behavior of these elements is related to the fact that each has 7 valence electrons (Table I). The re7 valence electrons requires a rather as shown by the value of the ionization high potential, potential of the gaseous atoms. This group tends to add an extra electron so as to produce the octet of the noble gas
end of
moval
of
one of the
element of next higher atomic number (Chap. II). With increasing size of the atoms, i.e., going down the periodic group, the attraction for the electrons decreases, as is shown
by the decreasing ionization potential and electron

156
affinity.
1]
GROUP
VII.
THE
HALOGENS
157
because of their high electron affinity the halogens are = 2X~, although much 2 + 2e~ powerful oxidizing agents, of the energy of the reaction in water arises from the energy of hydration of the negative ion. Fluorine not only has the
largest electron affinity, but, due likewise to its small size, the ion has the highest energy of hydration; consequently fluorine is the most powerful oxidizing agent the chemist
can prepare. These elements, with the exception of fluorine, also give compounds in which their oxidation state is positive, as
illustrated
by the
following:
assume that the halogen has lost electrons to the oxygen in such compounds, for the electrons are probably in reality shared by both, as indicated by the
It is arbitrary to
electron formulas, such as
H:0:C1::
o \J
it is obviously untrue that the actual 7. The concept of the the chlorine atom is charge upon 7 is most useful in correlating oxidaoxidation state of tion and reduction reactions. The half reaction which relates chlorine and perchlorate in aqueous acid solutions is,
From
this picture,
iCl a
+ 4H O = ClOr +
2
8H+
7e-
Thus the oxidation
of the element to perchlorate involves the loss of seven electrons. Actually this loss is shared between the chlorine and the oxygen but for simplicity we ascribe all of it to the chlorine and say the oxidation state The concept of the formal charge (cf Ill 7) which is 4- 7.
.
158
REFERENCE
[Ch.
assumes that the electrons of uie bond are equally shared by the two atoms, gives an approximate value for the actual charge upon each atom. While the formal charge is useful
in correlating many properties such as acid strengths, its use in determining the electrons gained or lost in oxidation-
reduction reactions is considerably more complicated than use of the oxidation state concept since it would require a summation of the change in charge of all of the atoms in
In addition to the the reacting and product molecules. terms oxidation state and formal charge, it is frequently convenient to employ a term which describes the number of
electron pair bonds on the central atom.
The term
coordi-
frequently employed in this sense but in organic chemistry the term valence is used to express the number of bonds. For the example of chlorine in HC1O 4 the oxidation state is 3 and the 7, the formal charge is
is
,
nation
number
valence or coordination
is
number is 4. The tendency to form an octet with the valence electrons made evident in the free element by the formation of the
is
diatomic molecules in which the 2 atoms share their 7th

electrons, so that each
octet.
in at least partial possession of
an
:X:X:
expected, the bond grows weaker with increasatomic radius, as shown by the increasing ease of dising sociation, and also by the decreased constraint under which the shared electrons are held, which is evident from the increasing dielectric constant.
2.
As might be
Occurence.
The estimated per cent
in the earth's crust is: F, 0.1; Cl, 0.2; Br, 0.001;
of the halogens I, 0.001.
Sea water contains about 2 per cent of chloride ion, and 0.006 per cent of bromide ion. The greater portion of the fluorine is in the form of fluorspar, CaF 2 and cryolite,
,
Na AlF6
3
The occurrence
discussed under
halides
is
of great deposits of the alkali the alkali elements. In addition to
2]
GROUP
VII.
THE
HALOGENS
159
the alkali halides, there are found in nature chlorides, bromides, and iodides of the alkaline earths, silver, lead, cop-
mercury, and bismuth. The major portion of the bromine of commerce formerly came from the bromoper,
TABLE
PROPERTIES OF THE HALOGENS
carnallite,
O, of the Stassfurt (Germany) deposits, and from various American salt brines, especially those of the Saginaw Valley, Michigan. With the introduction of the modern method for the extraction of bromine from sea water, this source now supplies most of the American market. The principal source of iodine is the Chile
2 2
MgBr -KBr6H
deposits,
where it occurs largely in the form of iodate, and periodate, NaIO 4 The largest source in the 3 United States is from the oil well brines in California. Blood
NaIO
contains âpproximately 0.25 per cent chlorine as chloride
160
REFERENCE
[Ch.
ion,
and the
gastric juices 0.2 to 0.4 per cent free hydro-
chloric acid.
Iodine
is
found
in the various
human
tissues,
the thyroid gland containing the highest per cent. Many marine plants exercise a selective absorption of iodide, even in the presence of far greater concentrations of chloride and bromide; hence dried seaweed is another important source
of iodine.
was
Preparation and Uses of Free Elements. Fluorine prepared by Moissan (1886) by the electrolysis of potassium fluoride in liquid hydrogen fluoride in a platinum vessel. Cells with this type of electrolyte are still used but for large scale production a fused 2 electrolyte is generally employed, using a copper vessel and a graphite anode. Copper is attached by fluorine but the surface of copper fluoride protects the metal from rapid layer corrosion. The electrolyte melts around 250 C. and the cell is generally operated slightly above 275 C. At this
3.
first
KHF
considerable pressure of above the HF. As the cell operates, hy2 electrolyte: drogen fluoride is decomposed and it is necessary to regenerate the electrolyte by the addition of more gaseous
temperature there
is
HF
KHF = KF +
hydrogen fluoride. There is also an increasing use of cells with KF'2HF as an electrolyte at a temperature of 80 to 120 C. The development of the fluorocarbons has greatly increased the commercial production of fluorine. Chlorine. Although the greenish yellow fumes formed by the oxidation of chlorides by various oxidizing agents had long been observed, it remained for Scheele (1774) to clean up their meaning. He prepared chlorine by heating a mixture of manganese dioxide and hydrochloric acid. He considered the gas to be "dephlogisticated muriatic acid," meaning muriatic acid (hydrochloric) freed from phlogiston (the element of combustion). Davy (1810) established its identity as an element. Scheele's method is still the one usually used for its laboratory preparation.
It is also
prepared by dropping dilute
3]
GROUP
VII.
THE
HALOGENS
161
hydrochloric acid upon potassium permanganate: 2KMnO4 16HC1 = 8H 2 O + 2KC1 + 2MnCl 2 + 5C1 2 and by the action of dilute sulfuric acid upon bleaching powder:
CaCl(ClO)
+ H SO = CaSO + H O +
2
C1 2
prepared by the of brine as described under the preparation of electrolysis sodium hydroxide. The annual production in the United States is over 400,000 tons. From the equilibrium electrode potentials (Append. II), one would expect oxygen to be liberated upon electrolysis of a brine solution; and this is the case in low concentration of salt: Q.2N NaCl yields about 20 per cent oxygen and 80 per cent chlorine at the anode. However, the oxygen evolution requires a high overvoltage (Append. I), and in more concentrated solutions only 1 or 2 per cent of oxygen is liberated. The Deacon process, employing the oxidation of hydrogen chloride by oxygen (Par. 5), has been of some importance in the past. Attempts have also been made to operate the reaction, MgCl 2 + Ô 2 = MgO + C1 2 commercially at a high temperature. The magnesium oxide is reconverted to the chloride by hydrochloric acid.
is
,
Most
of the chlorine of
commerce
Approximately two thirds of the chlorine manufactured

used in bleaching, chiefly of pulp and paper. Large quantities are also used in water purification as a germicide, and in the manufacture of organic dyes, explosives, and chemicals. It is usually liquefied and sold in cylinders, or converted into bleaching powder, CaCl(ClO), by action upon lime (Par. 6). The chlorine is again liberated from the bleaching powder upon the addition of acid. It was used extensively in the World War, at first directly as a poison gas, and later in the preparation of most of the other war " mustard gas/' gases, such as phosgene, COC1 2 and
is
,
(C
C1)
2 S.
Bromine may be prepared from the bromides by any of the methods used for chlorine. It is recovered commercially
in
Germany from
the waste liquors of the potash industry,
162
REFERENCE
in
[Ch.
America from various salt brines. The method depends upon the oxidation of bromide by chlorine. A comand
mercial process has been developed for the recovery of bromine from sea water. Free bromine is liberated by chlorine, and precipitated as tribromoaniline upon the addi-
The process is capable of extracting a of bromine from 1,800 gallons of sea water. pound Liquid bromine is used in the preparation of most of the
tion of aniline.
bromides and other compounds of the element. Like chlorine, it is used in the preparation of intermediate products in the synthesis of organic compounds, an example being the lead -tetrae thy 1 now added in small amounts to gasoline
knocking." The major portion of the American bromine is consumed in this process ethylene dibromide is the intermediate compound which is first formed. Iodine is extracted from kelp by oxidation of the iodides with chlorine, or manganese dioxide in acid, or even by
to prevent
"
production of
principal source is, however, the Chile deposits containing sodium iodate and periodate. Iodine ~ is liberated by reduction with sodium bisulfite: 2IO 3
sulfuric acid.
The
+ SHSCV =
moved and
Iodine
is
I2
+ 5SO
by
+HO +
2
3H+:
it
is
then
re-
purified
sublimation.
used in synthesis of aniline dyes, and iodides are employed somewhat in photography. It is also used in medicine as an antiseptic; in alcohol solution, known as
tincture of iodine; in iodoform, CHIs; and as metallic iodides, in the prevention and cure of goiter, and other dis-
orders of the thyroid gland. 4. Physical Properties. Table I gives the colors of the elements in the gaseous state. In the liquid state, the colors
are,
of course, deeper.
in
luster.
Liquid bromine and iodine are

Solid iodine
is
opaque except
very thin layers.
dark
colors
grey with a slight
Solutions of chlorine and bromine in water

closely resembling those of the gases.
show
Iodine dissolves in
4]
GROUP
VII.
THE
HALOGENS
163
many
and
hfcxane,
solvents, such as carbon tetrachloride, chloroform, with a violet color resembling that of the
dielectric constant
is
vapor; but in solvents of high water and alcohol, its solution
such as
brown.
The
progression
in color in the gaseous halogens with increasing atomic weights is due to an absorption band, which in fluorine is nearly all in the ultraviolet, removing only a little of the
end of the spectrum, thus causing the transmitted light to have an excess of the complementary color, yellow. With chlorine this band has moved down into the blue, and so on, until with iodine the band removes the middle portions of the visible spectrum allowing only red and violet light to be transmitted.
visible light at the violet
The density
cules of 2
atoms each, which
in the gaseous state corresponds to moleis confirmed by the figures for
Heated to sufficiently high temperatures, the diatomic molecules gradually break down into single atoms. The dissociation of iodine in this way
the same elements in solution.
becomes noticeable below 700. Progressively higher temperatures would be necessary for the corresponding dissociation as we go
from iodine to the lighter

"70
90
110
130
160
170
T C
FIG.
1.
Temperature-pressure diagram
of iodine
halogens, as indicated by the dissociation constants and heats of dissociation
given in Table I. be melted at 1 atmosphere Although may pressure, it sublimes without melting below a pressure of 100 mm. as is indicated in the phase diagram, Fig. 1. The halogens, with the exception of fluorine, are soluble in water (Table I). Chlorine and bromine form the hyC1 2 -8H 2 O and Br 2 -10H 2 0. The former is stable up drates,. to 28.7 under a pressure of 5 atm. of chlorine, and the latter to 6.2 under a pressure of 93 mm. of bromine vajror.
solid iodine
164
REFERENCE
[Ch.
Above 28.7,
chlorine under pressure forms with water two liquid layers. Bromine likewise forms two liquid layers, but the lower layer contains only a very small amount of water,
0.04 per cent at 10. 5. Reactions of the Halogens. The chemical behavior as related to atomic structure, has been discussed in Paragraph 1. Fluorine and chlorine are capable of oxidizing all
metals, while bromine and iodine can oxidize all but the noblest. The products of these reactions are halides. The halogens do not react directly with oxygen or nitrogen.
Fluorine reacts directly with all other elements except nitrogen, oxygen, chlorine, and the noble gases; and chlorine with all but these and carbon. Bromine and iodine are
less reactive.
reactions of the halogens with hydrogen are discussed in detail under the hydrogen halides. The halogens
The
upon many hydrocarbons, displacing hydrogen and forming the halogen acid e.g. CH 4 + C1 2 = CH 3 C1 + HC1. They also unite directly with many unsaturated compounds: C 2 H 4 + C1 2 = C 2 H 4 C1 2 and CO + C1 2 = COC1 2 They readily oxidize sulfur in most of its compounds: e.g. CS 2 + 2C1 2 = CC1 4 + 2S. Excess of chlorine (or bromine
act
:
but not iodine)

tion.
will oxidize sulfur to sulfate in
water solu-
TABLE
II
OXIDATION- REDUCTION POTENTIALS OF HALOGEN-HALIDE COUPLES
+ e~ Br- - iBr + e~ Cl~ - id + e~ FJF + eI-
VOLTS 25
JI 2
- 0.535 - 1.07 - 1.359
- 2.87
The oxidation-reduction potentials (Table II) of the free elements to the halide ions are extremely important, especially in connection with the general table (Append. II)
in predicting
iomde,
I""
many Br 2 =
reactions.
Thus, bromine
will oxidize
JI 2
+ Br~~, but will not oxidize chloride
5]
GROUP
VII.
THE
HALOGENS
165
or fluoride; and all of the halogens except iodine will oxidize ferrous ion to ferric: Fe ++ = Fe +++ 0.77 volt. e~~,
The halogens undergo two important

water:
(1)
reactions with
(2)
X +H X +H
2 2
,
2 2
= 2H+ + 2X- + |0 2 = H+ + X- + HXO

for reaction (1) in volts are:
,
The
potential values at 25
,
2,
2.0; C1 2 0.6;
direction).
Br 2 0.3, and I 2 0.3 (i.e., in the reverse Thus fluorine reacts vigorously with liquid
;
water, liberating not only oxygen but ozone chlorine reacts slowly in sunlight, liberating oxygen. On the other hand, moist hydrogen chloride gas reacts with oxygen with the
aid of a catalyst to give a detectable amount of chlorine. Bromine liberates oxygen only very slowly from water, and
the reaction is reversed if the hydrobromic acid has a high concentration. Iodine, on the other hand, is liberated from
a solution of hydrogen iodide by oxygen, the speed of the

reaction increasing rapidly with an increase in hydrogen ion concentration.
At a temperature of 450, an equilibrium is reached between chlorine, steam, hydrogen chloride, and oxygen by means of which it is possible to convert two thirds of the hydrogen chloride into chlorine. This is the basis for the Deacon process once used for the manufacture of chlorine. Hydrogen bromide is completely oxidized to bromine at
this temperature.
Reaction (2), the hydrolysis of the halogen, likewise takes place less completely, the higher the atomic weight of the halogen. In the case of fluorine the reaction cannot be
observed because of the rapidity of reaction (1). With the other halogens a reversible equilibrium is established. At 4 25, the equilibrium constants are: for C1 2 4.8 X 10~ for 9 13 The hydrolysis may in Br 2 5 X 10~ for I 2 3 X 10" the presence of acid, and every case be largely repressed by
,
increased
by the addition of alkali. Thus, hydrogen chloride
166
REFERENCE
[Ch.
added to hypochlorite liberates chlorine; and chlorine in sodium hydroxide solution is converted completely into chloride and hypochlorite. For a O.OlAf C1 2 solution, the above equilibrium constant corresponds to about 85 per
cent hydrolysis. The electronic picture of the hydrolysis consists of a splitting of the halogen molecule and a union
of the positive halogen
atom with water.
Electron formulas
:X:X: +
H:6:H=
2
+H+
X O
:
Ordinary formulas
X +HO
2
+ H+ + XOH
III
TABLE
SUMMARY OF IMPORTANT REACTIONS OF HALOGENS
X=
X
2
2 2 2
halogen
cf. cf.
X X
nX 3X 2 5X 2
2
H - 2HX H O = 2HX H - H+ + 2M = 2MX n

2
2
2
HXO
cf.
Par. 7 Par. 6 Par. 6
2P = 2PX 3 2P = 2PX 5
With most metals Also with As, Sb, Bi Not with I 2 Also As, Sb with and C1 2
.
F2
X + RH = RX + HX mX + 2C n H m = XmHX + 2nC X -f CO - COX X + SO - SO X X + H S - 2HX + S X + 2S = S X

2
2
RH many organic
hydrocarbons
2
2
At high temperature. Less readily with Br 2 and I 2 With C1 2 and Br 2 With F 2 and C1 2 Excess H 2 S With C1 2 and Br 2 F 2 forms SF 6 Clj
.
also forms
SC1 4
4X 2
I2
3X
-2S + 21+ 8NH + - 6NH X + N = NC1 + 4H + + 3C1~ 3C1 + NH 2X + Ti0 + 2C - TiX + 2CO
42
+S + 8X~
2 2
+
-f
8
10OH- = 2SO 4
4
5H 2O - S
Neutral or slightly acid solution
With F 2 C1 2 Br 2 I 2 forms NIa-NHs with NH 8 With C1 2 and Br 2 Also SiO 2 Cr 2Oi,

, , .
etc.
COMPOUNDS OF THE HALOGENS

In view of the great difference in the electronegative character of the halogens, it is not sur6.
Halogen Halides.
6]
GROUP
more
VII.
THE
HALOGENS
167
more
positive form compounds with the Thus, iodine forms IF7 (m.p. 5), IF 5 negative. (m.p. -9.6), ICl (2 forms m.p. a 27.2, 013.9), IC1 3 (m.p. 33), and IBr (m.p. 36); and bromine forms BrF 5 (m.p. -61.3), BrF 3 (m.p. 9), BrF (m.p. -33) and BrCl 66) and chlorine forms C1F 3 (m.p. (m.p. 83) and GIF (m.p. The positive character of the larger 154). halogen in these compounds is indicated, for example, by
electrolysis of liquid iodine chloride, ICl, and also by its sblution in sulfur dioxide, whereby iodine is liberated at the
prising that the
cathode, and chlorine at the anode. Hydrolysis gives the corresponding oxy-acid of the positive halogen, and the halide ion of the other. IF 5 + 3H 2 O = IOr + 5F~ + 6H+.
Because of the instability of the lower oxy-acids, the first step is not always realized: thus, SIC1 + 3H 2 O = 2I 2 + SCI" + ICV + 6H+ Iodine monochloride is formed by the direct action of
chlorine
upon
2
iodine,
ICl
is
+H
O.
By
HC1 reaction, HIO the latter reaction, iodine monochloand by the
ride
often formed through the reduction of iodates, or the
oxidation of iodides in moderately concentrated hydrochloric acid. It hydrolyzes in dilute acid. The chloride reacts with excess chloride ion to form the
complex ion
IC1 2
- = ICl(aq.)
Cl-
K
-
and the potential

ion,
of the oxidation of iodine to the
complex
2C1~
is
il,
IC1 2
e~
1.06 volts. (Cf. Par. 18.) If the formation of given as iodine monochloride in concentrated hydrochloric acid is accompanied by the liberation of chlorine, iodine trichloride, IC1 3 results. Salts, such as KIC1 4 are known. 7. Hydrogen Halides. Preparation. The hydrogen halides may be formed by direct union of the elements. As
,
,
168
REFERENCE
in
[Ch.
= 2HX, deTable IV, the reaction: 2 + H2 creases in energy with increasing atomic weight of the halogen. Fluorine and hydrogen combine instantly, even at a 253 C., where fluorine is solid and hytemperature of drogen liquid. The rate of combination of hydrogen and chlorine is slow in the dark, but takes place with explosive violence in the sunlight, or at 250 C. The increased speed under these conditions is doubtless due to the absorption of
shown
radiant energy by the chlorine molecule, and the more rapid reaction of this activated molecule. Of course, as soon as a few molecules react, enough energy is liberated to acti-
many molecules. Some idea of the force holding the molecules together is given by the consideration that the formation from hydrogen and chlorine involves the dissociation of C1 2 56,900 cah, and H 2 103,730. The reactions of hydrogen with bromine and iodine are very slow at room
vate
HC1
temperature, and are catalyzed by light and by platinum at higher temperature.
TABLE
IV
PROPERTY OF HYDROGEN HALIDES
Hydrogen fluoride and chloride are usually prepared by the action of the less volatile sulf uric acid upon a halide salt,
8]
GROUP
VII.
THE
HALOGENS
169
such as
process
CaF 2 and NaCl.

is
the reaction
(cf.
the
first
In the case of hydrogen chloride, step in the Le Blanc carbonate

acid sulfate
,
IV
13).
The
is
first
NaCl + H 2 and the heated to a temperature of about 500, in order to complete the second step: NaCl + NaHSO4 = HC1 + Na 2 SO4 Be:ause of the oxidation of bromide and iodide by hot con-
SO4 = HC1 + NaHSO4
formed: mixture is
.
2HI = I 2 :entrated sulfuric acid, S0 2 2H 2O, 2 S0 4 this acid is replaced usually by phosphoric acid in the preparation of hydrogen bromide and iodide. The acids may be
prepared by the hydrolysis of the halides of the more negative elements, such as phosphorus, sulfur, or arsenic: PBr 3 + 3H 2 O = 3 PO 3 + 3HBr. The halides of the noble
metals may be reduced with hydrogen at a high tempera= 2Ag ture to form the hydrogen halide: 2AgCl + 2 + 2HC1. These acids are also formed by the action of the
H
6
halogens upon
many organic hydrocarbons: C H + Br2 = CeH 5 Br + HBr. A solution of hydrogen iodide is con6
veniently prepared by the action of hydrogen sulfide upon a suspension of iodine in water: 2 S + I 2 = S + 2HI(aq.). With gaseous HI this reaction is reversible.
8.
Properties.
The hydrogen
halides are
all
colorless
gases; they possess a disagreeable pungent odor, fume strongly in moist air, are extremely soluble in water; their
water solutions, with the exception of hydrogen fluoride, are strongly acidic. The water solutions are called hydrofluoric
acid, hydrochloric acid, etc. In the pure liquid state, have a low electrical conductivity, of about the same
they
mag-
nitude as that of pure water. The approximate values for the dielectric constants of the liquids indicate that the electrical polarization decreases with increasing molecular
Hydrogen fluoride gas polymerizes, forming (HF) At 20 C. and 745 mm., 80 per cent of the HF is so polymerized. This property is not shown by the other gases. The water solutions exhibit the phenomena of boiling point maxima. The temperature composition diagram for
weight.
fl
'
170
REFERENCE
[Ch.
hydrochloric acid is given in Fig. 2. The curve represents the temperature at which a given composition of the acid will boil, i.e. the temperature at which the sum of the pressures of hydrogen chloride
and
water
equals
atmos-
pheric pressure. solution boils, its composition changes toward that of the maximum boiling mixture.
is
As a given
When this composition
reached, the solution boils
without further change in composition. The composition of the
maximum
boiling
FlG.
2.
Boiling point-composition
mixture depends upon the total pressure. For hydrogen chloride, 1 atmosphere, the value is 20.24 per cent HC1 and the temperature 110; for 2,500 mm., the composition is 18 per cent; and for 50 mm.
it is
curve for HC1.
tage
23.2 per cent. Advanis often taken of these
fixed concentrations to prepare acids of known concen-
trations for quantitative analysis.
Hydrogen chloride forms

three definite hydrates, as
indicated
eutectic,
FIG. 3.
in
Fig.
is
3.
The
86,
remark-
The system water-hydrogen

chloride.
ably low. Hydrogen bromide forms a di-, tri-, and
tetrahydrate and hydrogen iodide, tri-, and tetrahydrates. The ionization of these acids in dilute solution is 100 per cent, as judged by the lowering of vapor pressure and freez;
ing points, and by electrical conductivity. The apparent ionization at higher concentrations is discussed in
GROUP
VII.
THE
HALOGENS
171
pendix IV. Hydrofluoric acid is much weaker than the = 7.2 X 10~4 ). In fairly other acids (HFaq = H+ + F~, concentrated solutions, it forms the ion HF 2 ~ (F~~ HF = 5.5). In dilute solutions, its heat of neutral= HF 2 ~,
ization
acids,
is about 3 kcal. more than that of typically strong which is unusual, as the heat of neutralization of
other weak acids
is less
than that
of strong acids. The change of concentration of hydrogen ion in hy-
drochloric acid,
is
upon
titration with
hydroxide, 9. Uses. is used in etching glass. This remarkable property results from the action
of hydrogen fluoride upon silicon di4HF = SiF 4 2H 2 O. oxide: SiO 2
given in Fig. 4. Hydrogen fluoride
The
5
cc.
silicon fluoride escapes as a gas.
Etched designs, such as buret grad10

15
uations, are
made by covering
which
is
the
NaOH
of
glass with paraffin,
is
scraped
FIG. 4.
Titration
HC1
then treating with a solution of the acid. A mixture of ammonium fluoride and hydrogen fluoride is used in frosting glass. The acid is also used in
quantitative analysis, in dissolving complex silicates, since most silicates are decomposed through the removal of the
with
NaOH.
away where
etching
desired,
and
has certain application in the curing of crude rubber, in cleaning the exterior of stone buildings, and in cleaning castings. Hydrochloric acid is used in the preparation of metal
silica. .It
chlorides, especially those of zinc and tin in cleaning metal surfaces, particularly iron before galvanizing; and in the
;
manufacture of
materials.
10.
glue, soap, glucose, dyes,
and many other
Halides and Halide Ions.
Fluoride.
The
fluorides
of lithium, the alkaline earth,
and the rare earth metals are
172
REFERENCE
BOOK OF INORGANIC CHEMIblKY
ILh.
sparingly soluble. Fluoride forms more stable complexes than do the other halides with small positive ions, for ex-
A1F6 These complexes are analample, BF4 ~, SiF6 to the corresponding oxygen acids, and their stability ogous is doubtless due to high electrostatic attraction for the small fluoride ions. On the other hand, the fluoride ion is not as 2), and does not polarizable as the larger halides (cf. VII form coordination complexes with the ions of the readily
,
noble metals. The metal fluorides form acid salts of the type 2 and the crystal structure of these comand even 3 F4 pounds indicates that the hydrogen ion serves to bind two
KHF
KH
fluoride ions together:

:
11. ^hloride.^. Among the most important sparingly soluble chlorides are those of Ag+ Hg 2 ++, T1+, Cu+, Pb++,
,
Au+, Pt++, Pt++++, SbO+ and BiO+
The solubility of all metallic chlorides is decreased by a small excess of chloride ion, but a larger concentration often leads to an increase in solubility through the formation of
complex ions. The alkali and alkaline earth elements do not form complex chlorides, but practically all of the subgroup and transition elements do. Thus ions of the type [XCl6]~ 6+n are formed by the + 3 ions of the following elements: Al, In, Ir, Mo, As, Rh, Sc, Tl, and V; the +4 ions of: Ge, Hf, Ir, Os, Pd, Pt, Pb, Re, Sb, Si, Sn, Ti, Tl, and Zr; and the + 5 ions of Cb, Sb, and Ta. Ions of the type [XCl4 ]-4+n are formed by the + 2 ions of Be, Co, Cu, Cd, Hg, Pd, Pt, and Zn, and by the + 3 ions of Au, B, Bi, In, Re, Tl, V, and Y. With Ag+ and Cu+ the complex chlorides are The ions [XCl 4 ]-6 +n XClr, XC1 8 and possibly XC1 4 4 are octahedral but the [XCU]^ are of the two types, tetrahedral and square planar. There is some evidence for the formation of trichloride
.
" "11 1
111
GROUP
VII.
THE
HALOGENS
173
when chlorine is passed into concentrated hydrogen chloride (see Triiodide below). Certain of the chlorides, especially the volatile chlorides
Cl 3
of metals of higher valence,
may
of chlorine
e.g.
upon a heated mixture

2C1 2
be prepared by the action of the oxide and carbon
TiO 2
Chlorides of
2CO. the non-metals, e.g. CCl 4 PCl 6 SCl 4 are

,
, ,
2C = TiCl 4
discussed under these elements.
Bromide. Bromide ion is very similar to chloride ion in the character of its slightly soluble compounds and complex ions, though in general the sparingly soluble bromides are somewhat
chlorides.
less soluble
than the corresponding
Alkali bromides are usually prepared from bromine, by first forming ferrous bromide by action of bromine upon
iron,
the
and then carrying out the double decomposition with alkali carbonate: e.g. FeBr 2 + K 2 CO 3 = FeCO 3 2KBr. + Iodide. The iodide ion, being the largest and most easily
(cf.
polarized
salts,
VII
2) of
the halides, forms very insoluble
and very stable coordination complex ions with the subgroup metals. The stability of many of these compounds is limited, however, by the ease of oxidation of iodide to the free element. The method of formation of the
alkali iodides is similar to that of the bromides, vide supra. Iodide ion readily dissolves iodine with the formation of
triiodide: I"
1.4
+
3
12
(aq.)
I 3 ~~,
10"~
at
25. This reaction
the constant (I-)(I 2 )/(I 3 ~") is important as a means
of bringing iodine into aqueous solution. Higher polyiodides are formed in very concentrated solutions.
In neutral solution, iodide is not readily oxidized by oxygen in the air; but in acid solution, the reaction becomes O 2 4H+ = 2Ir + 2H 2O. The quantitarapid: 61-
tive oxidation of iodide
HO
2
or
KMnO
4,
is
by powerful oxidizing agents, e.g. extremely important in quantitative
analysis (Par.
174
12.
REFERENCE

of
[Ch.
Oxygen Compounds
forms the fairly stable oxide,

the oxides
F O2
2
Halogens. Fluorine at low temperatures and F 2 O3. Bromine forms no stable oxides,
the
F 2 O, and
though the unstable oxides Br 2 O and BrO 2 have recently been prepared. Chlorine forms the oxides C1 2 O, C1O 2 and CUO?; and iodine, the oxides I 2 O 4 and I 2 O 5 A number of additional oxides as ClOs, C1O 4 and I 2 Os have been described, but they are extremely unstable. None of these oxides are formed by direct union of the elements. The oxides with an odd oxidation state of the halogen are anhy,
drides of the corresponding acids. The oxygen acids of the halogens are given in the following summary. The halous acids and their salts are of the least importance. Indeed the
existence of
HBrO 2 and HIO 2 an intermediate reaction step.
is
but momentary, usually as
TABLE v
OXYGEN ACIDS OF THE HALOGENS
TABLE VI OXIDATION-REDUCTION POTENTIALS OF HALOGEN ACIDS AND IONS

VoltS 2 5
12]
GROUP
VII.
THE
HALOGENS
175
is
are powerful oxidizing agents, as indicated in the table on page 174, which gives the potential in volts for their reductions to the elements in
The halogen oxyacids
These values be used to calculate the potentials of the reduction in The potential diagrams for all of the halogens are steps.
acid
in alkaline solutions.
and to the halides
may
summarized
in Par. 23.
Periodic acid
is
the most powerful
oxidizing agent of all the oxyacids. Since the oxyacids of chlorine and bromine are sufficiently powerful oxidizing agents to liberate oxygen from
- 1.23 volts), it follows 4H+ water (2H 2 O = O 2 4e~, that water solutions of these acids are unstable. These decompositions are slow, but are catalyzed by certain sub-
stances.
from the table that the oxidizing potentials of the halates decrease with increasing atomic weight, so that iodine will replace bromine in bromate, and ~ bromine will replace chlorine in chlorate: e.g. 2BrO 3 + 12
It
may
also be observed
= 2IO
~~
3
solution, actions, they are in reality complicated oxidation-reduction reactions.
Br 2 The reactions take place in highly acid and while they are often called replacement re.
With the exception

;
the oxygen halide (cf. Table II) hence, these acids are reduced by the halide ion. H+ HC1O Cl~ = C1 2 IOr 2 O;
of perchloric acid, the potentials of acids are greater than those of the halogens to
+H
+ +
+
H+ 3 proaches the stoichiometric equation: 5HXO = 2X 2 2H 2 O. The speed of decomposition increases in order from hypochlorous to hypoiodous. In the rapidly case of chlorate ion, we encounter instability with respect to perchlorate and chloride ions, according to the equation
unstable in regard and reduction into halate and halide; 2X~. Because of the reduction of the halide as mentioned above, this
is
6H+ + 51The + 1 state
3I 2
+ 3H
O.
to its
own
oxidation
thus 3XO~ = 3 the oxygen acids by reaction in acid ap-
XO
~~
XO +
~~
176
REFERENCE

Cl"~.
[Ch.
4C1O3~"
state.
13.
3C1O4~~
This occurs readily in the fused
Oxides of Fluorine.
The
oxide
(probably better
called the fluoride),
a dilute solution
of
2 O, is formed by passing fluorine into sodium hydroxide.
2F 2
+ 2OH- =
F 2O
2F-
+HO
2
The
146.5 and in the absence of reducing a stable gas at room temperature. It does not reagents act with water but is a very powerful oxidizing agent.
oxide boils at
is
HO+
2
2F- = F 2 O
2H+
4<r
E = -
2.1
and an even higher
potential
may
be given for the reaction
2F~
but
K> 2 = F 2 O
2e~
E = O
,
3.1
it appears unlikely that the second reaction can be realized experimentally. The dioxide, F 2 2 may be prepared at low temperatures by the direct combustion of
oxygen and fluorine under the activation of an

discharge, O 2 57 boils at
electrical
F2 = F2O 2
is
It
melts at
163.5
C. and
C. but
highly explosive above
14. Chlorine Monoxide and Hypochlorite. monoxide, C1 2 O, is the anhydride of hypochlorous acid, H 2 O = 2HC1O, is HC1O. Its reaction with water, C1 2 O
100 C. Chlorine
reversible.
gas, at 1 atmosphere and 0, is in equilibrium with a solution containing about 200 volumes of the
The
gas per volume of solution. It is most conveniently prepared by the action of chlorine upon finely divided mercuric 2C1 2 = C1 2 O oxide: 2HgO Hg 2 OCl 2 The reaction is carried out at about 0, at which temperature the gas condenses to a liquid. The gas and liquid have a deep yellowish
red color, and are highly explosive. The hydrolysis of chlorine (Par. 5) yields hydrochloric acid and hypochlorous acid. The equilibrium is displaced by hydroxide through the neutralization of these acids:
14]
GROUP
VII.
THE
HALOGENS
C1O-.
177
C1 2
+ 2OH- = H O +
2
Clis
A solution containing
chloride
and hypochlorite
ysis of a solution of
NaCl
easily prepared by the electrolin a cell permitting the chlorine
produced at the anode to react with the OH~ produced at the cathode. This solution is a cheap, efficient, and widely used disinfectant and bleaching agent. For household use, it can be purchased under the name of "chlorox."
When
4-
chlorine
is
occurs which
CaCl(ClO). The resulting product, represented by CaCl(ClO), is known as "bleaching powder," or "chloride of lime" and is a complex mixture of CaCl 2 Ca(ClO) 2 and Cu 3 (OH) 4 (ClO) 2 Upon solution in water it gives the corresponding ions; hence, when an excess
2
,
Ca(OH) 2 =
HO+
is passed over slaked lime, a reaction closely related to the one given above CU
:
of acid
added, chlorine is liberated, corresponding to the shift of the hydrolysis equilibrium of chlorine. Bleaching powder is extensively used for bleaching and disinfecting. Any solution containing both Cl"" and C1O~~ can be made to yield chlorine in almost any desired concentration by suitably fixing the hydrogen ion concentration. However
is
small the equilibrium concentration of chlorine, it will nevertheless be approximately maintained as the chlorine
is
the
used up. Such a solution is name "Dakin's solution."
much used
in surgery
under
v
One equivalent of acid, acting upon bleaching powder, liberates the weak hypochlorous acid, HCIO, which may be
distilled
from the solution and thus separated from chlo-
ride ion.
The
dissociation constant of the acid
is
5.6
10-*.
familiar odor of bleaching powder is due to hypochlorous acid liberated by the carbonic acid of the air.
The
Hypochlorite solutions readily give off oxygen (Par. 5) in the presence of a catalyst, e.g. cobalt hydroxide. Heated in the absence of a catalyst, the following reaction occurs: 3C1O- = C1O 3 ~ 2Q-. The rate is increased if the solu-
tion is slightly acid-
178
REFERENCE
[Ch.
16. Chlorites and Chlorine Dioxide. Although chlorine dioxide and the chlorites are of different oxidation states, they are discussed together because of the formation of
chlorite
2OH- + 2C1O = C1O 2- + C1O

2
by the
reaction of the oxide in alkaline solution:
+H
;
O. Chlorine dioxide
i.e.
is
one of the few "odd molecules" :O:C1:O:,
posof
sessing
an odd number
of electrons
and the mechanism
the above reaction may be considered to be the transfer of the odd electron from one molecule of the oxide to another, ~ + The latter adds a molecule of forming C1O 2 and C1O 2 hydroxide to form HC1O 3 Chlorous acid is unstable except in very dilute solutions. The sodium salt NaClO 2 may be
. .
obtained commercially. The formation of chlorine dioxide from chloric ac'd is mentioned below (Par. 16). It may also be prepared by the
action of chloric acid
upon
2
oxalic acid:
2HC1O 3
+HCO
2 2
.
commercial process chlorine dioxide by the action of chlorine upon dry prepares The sodium chlorite: NaClO 2 + iC! 2 - NaCl + C1O 2 dioxide is used for bleaching flour, paper and textiles and in controlling blue mold.
2
2
= 2C1O
+ 2CO + 2H
O.
A new
Approximate values
2H O 40H2
for the potentials of the dioxide are

VOLTS 26
4- Se~
+ +
ClCl-
- CIO = C1O
2 2
4-
4H+ 2H 2
+ 5e~
-1.50
0.8
16. Chloric Acid and Chlorates. Chlorates are easily prepared by decomposition of the hypochlorite (Par. 12). The process may be carried out, either by passing chlorine into hot alkaline solution, or by the electrolysis of a hot chloride solution with agitation so as to bring the chlorine from the anode into contact with the hydroxide of the cathode. Chloric acid decomposes upon distillation, and cannot be prepared in the pure state. A solution may be obtained by treating a solution of barium chlorate with dilute sulfuric ~ =
acid:
Ba++
2C1O 3
+ 2H+ + SO
"
BaSO4 + 2H+
17]
GROUP
VII.
THE
HALOGENS
179
its salts.
It is a strong acid and is much less stable than In addition to the decomposition into perchlorate and chloride and into oxygen and chloride, it may decompose according to the equation: 4HC1O3 = 4C1O2 + C>2 4- 2C1O3~~.
If concentrated sulfuric acid is added to solid the above reaction takes place, and usually the chlorate, C1O2 formed explodes with great violence. Potassium chlorate is the most important salt of chloric
2H2O.
acid.
While readily soluble in hot water, its solubility is 3.1 g. per 100 grams of water at 0. Advantage is taken of this behavior in preparing potassium chlorate by adding
but
i
potassium chloride to a hot solution containing chlorate ion made from calcium hydroxide and chlorine, and then
cooling.
Potassium chlorate decomposes at moderate temperatures as follows: 2KC1O 3 = 2KC1 + 3O 2 This reaction is catalyzed by manganese dioxide, and furnishes a convenient
.
laboratory method for the preparation of oxygen. If carefully heated to avoid the evolution of oxygen, potassium chlorate may be converted into the perchlorate: 4KC1O 3
= 3KC1O 4
The
KC1.
power of potassium chlorate renders it useful in making matches and pyrotechnics. Explosive mixtures may be made, using potassium chlorate with combusoxidizing
substances such as charcoal, sugar, or sulfur; they are too treacherous to be of practical value. A solution of potassium chlorate is sometimes used as a gargle in throat intible
fections.
All of the chlorates are at least moderately soluble. Lithium chlorate is one of the most soluble of all salts, 100 g. of water dissolves 315 g. of the salt at 18. As mentioned in 17. Perchloric Acid and Perchlorates.
the previous section, perchlorates
solutions:
fully heating chlorates. anodic oxidation in the electrolysis of concentrated chlorate = 2H+ 2e~.
may be prepared by careThey may also be prepared by'

ClOr +
C1O 8
+HO
2
Although
180
REFERENCE
[Ch.
only requires a calculated potential of is difficult to find an oxidizing agent of bringing it about, since the oxidizing agent must capable at the same time be more powerful than chlorate peroxysulfuric acid or sodium bismuthate may, however, be used for this purpose. Perchloric acid may be distilled from a solution formed by the addition of sulfuric acid to a perchlorate.
this half reaction
about one
volt,
it
This reaction is subject to violent explosions. The anhydrous acid is best prepared by the action of nitric and hydrochloric acids upon a solution of ammonium perchlorate. The pure acid is a volatile liquid at ordinary temperatures, and decomposes at 92 under atmospheric pressure. The acid reacts explosively with strong reducing agents. It combines with water to form the solid hydrate, HC1O 4 -H 2 O, with the evolution of much heat. It is interesting to note that this hydrate, OH 3 C1O 4 has the same crystal structure
,
addition of phosphorus pentoxide to acid, cooled below 0, results in formation of perchloric

as
4
NH C1O
4.
The
P 2 O 5 = 2H 3 PO 4 3C1 2 O 7 perchloric anhydride: 6HC1O 4 This oxide is a colorless liquid which may be heated to its
82, without decomposition. onated, however, by a sudden shock.

boiling point,
It is easily det-
The perchlorates are safer to handle than the chlorates. They are used in matches, fireworks, and explosives. They
are as a rule readily soluble, potassium, rubidium, and cesium perchlorates being the least soluble. Due to its
slight solubility,
and
potassium perchlorate is easily prepared purified. It is probably the most important of the salts. If silver perchlorate is treated with bromine, silver bro,
mide and free perchlorate radical, C1O 4 result: 2AgClO4 + Br 2 = 2AgBr + 2C1O 4 This substance also has an odd number of valence electrons, and is extremely reactive and
.
unstable.
Hypobromite and Hypoiodite. The hydrolysis of the halogens decreases markedly with increasing atomic weight
18.
(Par. 5); however, in strongly alkaline solution both bro-
19]
GROUP
VII.
THE
HALOGENS
181
mine and iodine are almost completely converted into the and hypohalite. Hypobromous acid, and more especially hypoiodous acid are very unstable, decomposing within a few minutes into the halide and halate. They are
halide
also extremely
weak
acids.
In fact, the reaction,
IOH
HC1 =
IC1
+H
O, indicates certain basic tendencies
Hypobromites and hypoiodites decompose more readily than hypochlorites to give halate and much halide. The unstable monoxide, Br 2 O, has been prepared by the action of bromine upon mercuric oxide at 50: 2HgO + 2Br 2 = Br 2 O + Hg 2 OBr2 In addition to the methods of 19. Bromate and lodate. preparation analogous to the chlorine compounds, bromic and iodic acids may be prepared from the elements by the
in the latter.
.
action of powerful oxidizing agents such as hypochlorous,

chloric,
and
nitric acids,
and hydrogen peroxide.
Bromic
acid cannot be prepared in the pure state, as the concentrated solutions decompose, forming oxygen and bromine.
The bromates
and may
are in general less soluble than the chlorates, be distinguished from the latter by the insolubil-
ity of silver bromate.
They have some

and
is
industrial applica-
very soluble in water. It is most conveniently prepared in a pure state by the action of a slight excess of chloric acid upon iodine, or by the
action of hydrogen peroxide in acid solution
It
.
tions as oxidizing agents. Iodic acid is a white solid
upon
iodine.
may be dehydrated by careful heating to form the pentoxide, I 2 O 5 This is a white solid which may be heated to about 300 before decomposition becomes rapid. Sodium iodate, occurring in the Chile nitre beds, has been mentioned
as the most important source of the element. The iodates are much less soluble and much more stable than the other halates, and are easily distinguished from them by the insolubility of their barium and lead salts. Iodates in highly Neither the acid nor the acid solution oxidize chloride.
salts
show any tendency
to decompose to form the perio-
182
REFERENCE
[Ch.
X*
dates.
Potassium iodate and bi-iodate,
KH( 103)2,
are of
considerable importance in analytical chemistry (Par. 21), because of the quantitative reduction to iodine in dilute acid and to iodine chloride in moderately concentrated
hydrochloric acid by many reducing agents. The potential 1.23 volts corresponding to the for the latter reduction is half reaction
:
3H O +
2
IC1 2
= IO 3The
+ 6H+ +
oxide,
I2
4,
2C1-
+ 4<r
19.
Iodine Tetroxide.
O may be prepared
5I 2 O4
by the action of concentrated sulfuric acid upon iodic acid, It reacts similar to the preparation of chlorine dioxide.
with water according to
the
equation:
it
+ 4H O
2
= 8HIOa +
pound,
(I 2
I 2.
4
With
2
sulfuric acid,
forms a complex com-
O )H SO
4.
Strong oxidizing agents convert the iodates into periodates. There is a long series of polybasic periodic acids which may be considered as derived from the anhydride, I 2 O 7 by the addition of n molecules of water, I 2 O 7 -wH 2 O, where n has the values 1 to
,
20. Periodic
Acid and Periodates.
7: e.g.
2
I2
O + H O = 2HIO
7
I2
O + 2H O = HJ O
7
2 2
I2
+ 7H O = 2H
IO 7
The
existence of
acid,
somewhat doubtful, but the
IO 7 or its salts, is H 5 IO6 is probably the

7
,
,
principal constituent of the water solution. The constant 10" 4 and for the second about for the first ionization is 5
10~7
The second
involve the equilibrium, HJOe"" = IO 4 2H 2 O. The higher polybasic acids may be dehydrated to form the meta acid, HIO 4 but the anhydride, I 2 O 7 cannot be prepared, as
step of the neutralization appears also to
further heating causes decomposition into oxygen and the pentoxide. The fact that the iodine atom in periodic acid is
surrounded by as
chlorine
many
as six oxygen atoms, while the
atom
in perchloric acid is limited to four
may
be
correlated with the larger size of the iodine atom. The prepp ration of periodates is usually accomplished by + heating iodace with chlorine in alkaline solution: 2Na
22J
GROUP
Cli
VII.
THE
2
HALOGENS
3
183
+ IOr + 3OH- +
= Na
is
IO 6
+ 2C1~.
The product,
but moderately soluble. In highly acid solution the periodates are extremely powerful oxidizing agents, being capable of oxidizing manganous ion to 1.5 volts. permanganate, which requires a potential of Excess periodate, in even low acid concentration, is reduced ~ " to iodate by iodide: 2H+ + IO 4 + 2I~ = IO 3 + I 2
disodium paraperiodate,
With excess iodide, the product is triiodide. 2 O. 21. Analytical Properties. Advantage is taken of the insolubility of silver chloride, bromide, and iodide in both
the qualitative and quantitative determination of these halides (cf. VII Iodides and bromides are readily dis28). tinguished from chlorides by the liberation of bromine or
iodine
teristic colors
+H
by chlorine water, and the production of the characupon extraction of the free halogen with
disulfide.
carbon
The oxygen compounds of the halogens may be determined qualitatively by the reduction to the free element or halide, and identified as such. Quantitatively they may be
reduced by excess reducing agent, such as stannous chloride, or titanous chloride, and the excess reducing agent titrated with permanganate; or they may be reduced with excess iodide and the iodine formed titrated (at low H + ) with = 31" + S 4 O 6 thiosulfate: I,- + 2S 2 O 3
The reaction just given for the oxidation of thiosulfate by iodine or triiodide is one of the most important in chemical analysis.
provides a general method for the determination of oxidizing agents, as indicated above, by the addition of excess iodide and the titration of the iodine by
It
point indicator in this titration, soluble starch is added to the solution, giving a deep blue color as long as an appreciable concentration of iodine is
thiosulfate,
As an end
present. Strong reducing agents may be titrated by direct oxidation with triiodide. The most stable isotopes of element 85 22. Astatine. have the mass numbers 210 and 211 (cf. all XXII ), their
184
REFERENCE
[Ch.
being 8.3 hours and 7.5 hours respectively. Astatine 211 is readily prepared by bombarding bismuth with alpha-particles in the energy range of 21-29 Mev. Because of the very short half-life, all experiments on the chemistry of astatine have been carried out on minute quantities of the element. In general the concentrations in W 211 is an a-emitter solution have been less than 1Q~ M. At
half-lives
possible to follow the course of the element in a reaction by means of its radioactivity. However, chemical the behavior of an element in tracer amounts is often
it is
and
erratic,
and the observations so

.
far
made
are open to
rein terpretation
The element
270 C.
It is
in the zero oxidation state is fairly volatile

distillation
and may be separated from bismuth by
at
reduced by zinc or sulfur dioxide in acid 1 state and is oxidized by ferric ion, solution to the bromine and nitric acid to a positive state, probably HAtO. Like iodine the element is readily soluble in carbon tetraIn alkaline solution the element is chloride or benzene. unstable with respect to its disproportionation, probably
into
At" and AtCT.

1
+ completely precipitated with Ag using Agl as a carrier. There are two positive oxidation 1 and 5. Powerful oxidizing states, probably the in acid solution such as hypochlorous acid and agents peroxysulfate are required to oxidize the element to the higher state. An interpretation of the chemistry gives the following tentative values for the oxidation reduction
The
state
is
couples in acid solution
+ e-E = ca 0.3 H O + |At = HAtO + H+ + e~E = ca - 0.7 a = HAtOs + 4H+ + 4<rE = ca - 1. 3 2H O + HAtO The +1 (?) state does not precipitate completely with
At~ = |At 2
2 2
2
a carrier but the higher oxidation state carries completely with this precipitate.
silver iodate as
23]
GROUP
VII.
THE
HALOGENS
185
23. Potential Diagrams. For a comparison of the oxidation-reduction properties of the members of the halogen family, the following summary is given
:
Acidic Solutions:
F-
2.87
F
-1.36
C1 2
|
-1.62
-1.63
-1.21
Cl-
HC1O
HC1O 2
1.47
C1O 3 |
-1.19
ClOr
Br-
1.07
Br 2
|
1.59
1.49
H BrO
-1.52
BrOr
|
-0.53
I12
-1.45
-1.14
ml. 70
I0.r
At-
Basic Solutions:
Cl|
Br-
I(
AtI
- -- - - _ -----_ _ -- __
1.06
HIO
IC1 2
HJO
1.23
1.20
-(-0.3)
(-0.7)
At 2
HAtO
(-1.3)
(?)
AtO 8
(?)
2.85
1.36
0.40
0.65
0.35
0.36
ci, 0.88
cioI
cior
cior
cior
1.07
0.45
0.54
Br 2
BrO0.14
BrOr
0.7
0.53
0.45
12
10|
~ 10 3
ca
0.49
(-
0.3)
(0.2)
(-
0.3)
At 2
AtOI
AtO 3-
1-005)
Chapter XI
GROUP
1.
NITROGEN, PHOSPHOROUS, ARSENIC, ANTIMONY AND BISMUTH
V.
of Group V, nitrogen, phosphorus, arand bismuth, have a maximum positive senic, antimony, oxidation state of five in agreement with the presence of
five valence electrons. The nitrogen atom, the smallest of the group, shows strong tendencies to add three additional electrons and thus complete the octet; but this property decreases with increasing size so that bismuth forms no stable compounds in which it has a negative oxidation
The elements
state.
Nitrogen and phosphorus are non-metallic
in their
properties, but the heavier elements of the group are increasingly metallic. Each of the elements forms an acid
pentoxide, though the acidic nature of the oxide decreases markedly with increasing size of the positive ions. The
elements also form sesquioxides which are acidic with the lighter members, but become basic with the heavier. The elements of the group thus show a complete transition from
non-metallic to metallic character. Nitrogen, like the first member of other groups, differs in many respects from the other elements. For this reason, and also because its importance warrants a more detailed treatment, it will be considered separately. A further discussion of the group properties is given in Paragraph 40.
NITROGEN
2.
Occurrence.
is free
Four
fifths
2.
phere
nitrogen,
by volume
of the atmos-
All fertile soils contain the ele186
4]
GROUP
in the
V. NITROGEN,
PHOSPHORUS, ETC
salts, nitrates,
187
ment
form of ammonium
is
or nitrites;
a constituent of all proteins. The occurrence of deposits of alkali nitrates has been mentioned (cf. IV The amount of nitrogen in the primary rocks is so 23). small that nitrogen ranks among the less abundant elements, constituting but 0.03 per cent of the earth's crust
and nitrogen
and atmosphere.
Preparation. Atmospheric nitrogen is the cheapest source of the element, and large quantities are prepared commercially from the air by fractional liquefaction (cf.
3.
Ill
This process concentrates the argon somewhat 6). about 3 per cent), but the gas is sufficiently pure for (to most commercial purposes. Nitrogen may, of course, be prepared from the air by the absorption of oxygen by chemical agents, such as heated copper. Pure nitrogen is usually
prepared, either
3
by passing ammonia over copper

2
oxide:
2NH + 3Cuu = N -f 3H 2 O + 3 Cu, or by heating a solu~ tion containing ammonium and nitrite ions: NH 4 + + NO 2 = N + 2H O. Once the latter reaction is started, it pro2 2
ceeds rapidly or even explosively unless cooled. Other reactions producing nitrogen under appropriate experimental
conditions are:
MnO + 4NH NO = Mn(NO + 8H O + 4H O + N 2P + 5NH = 2H PO + 7H O + 5N CO(NH N0 + 2HNO

2
3) 2
+ 3N
3
(NH 4 ) 2 Cr 2 O 7 = Cr 2 O 3
3
2) 2
= CO
+ 2N + 3H
2
O.
The more impor4. Properties of Molecular Nitrogen. tant physical properties of atomic and molecular nitrogen are summarized in Table I. The gas is colorless and The low boiling point is indicative of the statasteless. of the molecule. Although the arrangement of the bility 10 valence electrons in the molecule is not known, the
formulae
:N;|N:
and
:N::N:
probably represent the two most important resonating states of the molecule. The. molecule is diamagnetic. The
188
REFERENCE

TABLE
[Ch. XI
PHYSICAL AND ATOMIC PROPERTIES OF NITROGEN
heat of dissociation is probably greater than that of any other diatomic molecule, and is doubtless the chief factor in its very slight reactivity. It may be calculated from thermal data, that at 8,000 C., the gas is only about 40 per cent dissociated into atomic nitrogen. Under the influence of a high voltage discharge, i.e. high velocity elecis "activated." Active nitroto be atomic nitrogen, in which one or more gen appears electrons are raised to higher energy levels. Active nitrogen
trons, the nitrogen molecule
continues to glow for some time after the discharge has been stopped. It combines readily with many elements, phosphorus, sulfur, sodium, etc., with which ordinary nitrogen does not react.
The more important

Table
II
reactions of the element are given in

in connection
and will be discussed further various compounds.
with the
TABLE
N,
-f
II
REACTIONS OF NITROGEN
N + O - 2NO N a + CaC CaCN N + 3Mg - Mg,N

2
a 2
3H - 2NH,
2
See ammonia See nitric acid See cyanamide process Also Li,N, Ca,N 2 BN, A1N, TiN,
,
etc.
Na + AUO, + 3C - 2AIN + 3CO Na 4- 4C + Na aCO, - 2NaCN 4- 3CO
See also
XHI
24
6]
GROUP
V.
NITROGEN, PHOSPHORUS, ETC
189
COMPOUNDS OF NITROGEN AND HYDROGEN

oxidation state
in which its and a trinitride with 3, 2, 1, an average polar number of 1/3. The most important of 3 compounds, ammonia and its derivatives. these are the The compound, NH2, exists only in the double molecule, N 2 H 4 hydrazine, and the compound NH is known only as the hydrate, NH 2 OH, hydroxylamine, and its derivatives.
6.
is
Nitrogen forms with hydrogen compounds
and
The probable
given below
:
electronic structures of these
compounds
are
H H
:N:
ii
2
H
+ H O->H:N :H :O :H
ii
H
ii
Hydrazine
2H :N--H :N:N :H
Ammonia
Ammonium
hydroxide
H
H N+
:
H 2O =
:N :O :H
,
:N::N::N:H
Hydrazoic acid
Hydroxylamine
The three nitrogen atoms in hydrazoic acid are linear, which corresponds to double bonds between the tetrahedral atoms, but there is probably resonance with other electronic
structures.
Ammonia was formerly the destructive distillation, in the absence of air, of hoofs, horns, and other nitrogenous organic substances; and the solution of the gas was called "spirits of hartshorn."
6.
Manufacture of Ammonia.
made by
ter,
Coal, due to its vegetable origin, contains nitrogenous matand one of the chief sources of ammonia has been the "by-product ammonia," from coke ovens and coal gas
works, in which ammonia produced by the distillation of the coal is separated from the other coal-tar products. The gas is usually washed with water to separate it from the tar, then with sulfuric acid which removes the ammonia as ammonium sulfate. Pure ammonia may be prepared from this by evaporation and treatment with calcium hydroxide.
190
REFERENCE

industrial
[Ch. XI
7.
One
of the
most important
developments of
recent years has been the production of synthetic ammonia through the direct reaction of hydrogen and nitrogen: 3H2 2NH 3 The reaction evolves 24,000 cal. hence, the 2
+N
formation of ammonia is favored by low temperatures, and because of the volume change, by high pressure (cf. Principle of Chatelier, Hildebrand, Prin. of Chem. p. 244), as
y
is
indicated in the following table.
TABLE
III
1
VOLUME PER CENT AMMONIA IN EQUILIBRIUM WITH A MOLAL MIXTURE OF N2 AND Hz
TO 3
The
rate of reaction
is
slow at the lower temperatures,
and the commercial process has been dependent upon the development of efficient catalysts. The Haber process, developed in Germany, employed according to the original patents, iron oxide containing other metals, such as molybdenum, uranium, or cobalt. Recently developed plants employ, as a catalyst, iron made by the reduction of fused iron oxide (magnetite) containing small amounts of both basic and acidic oxides, such as 0.5 per cent A1 2 O 3 and 0.5 per cent K 2 O; and operate at pressures of 100-200 atmospheres and temperatures of 550-600 C. The French Claude process attempts to utilize the greater yields at higher pressures by working at 600-1,000 atmospheres. Under these conditions, ordinary sheet iron is very permeable to hydrogen, and the containers must be constructed of The American production of special chrome-steel alloys.
10]
GROUP
V. NITROGEN,
PHOSPHORUS, ETC
191
synthetic ammonia, in 1946 was about 725,000 tons of contained nitrogen as compared to 220,000 tons of by-product
ammonia. 8. Another source of ammonia is calcium cyanamide, CaCN2, which is formed by the action of nitrogen upon
calcium carbide (Table II) at about 1,200. When treated with steam, cyanamide is hydrolyzed: CaCN2 + 3H 2 O
= CaCO 3 + 2NH 3
rectly as fertilizer.
Much
of the
The world production
cyanamide is used diof cyanamide in
1938 was 300,000 tons of contained nitrogen. 9. Attempts have been made to manufacture ammonia commercially by the hydrolysis of aluminum nitride in hot
sodium hydroxide solution: A1N

-f
NH
3.
The
in
nitride
is
made by
2 A1(OH) 8 aluminum oxide heating
+ 3H O =
and carbon
an atmosphere of nitrogen to about 1,700. The reaction is slow, and the process is unable to compete with the direct synthesis from the elements. Ammonia may also be prepared by the hydrolysis of sodium cyanide:
NaCN + 2H O = HCOONa + NH
2
3.
The historical laboratory method for the preparation of ammonia has been the reaction between an ammonium salt and a strong base (usually calcium hydroxide): NHS~
+ OH" = NH + H
3
O.
Physical Properties and Uses of Ammonia. Amboils at 78, has a critical tem33.4, melts at of about 133, and a critical pressure of 112 atm. perature The vapor pressure of the liquid at 25 is 9.90 atm., is easily liquefied by pressure at that temperature. ^lence'it v If the pressure upon the liquid is decreased to one atmos10.
monia
^5hfcre,
the temperature of the liquid, of course, falls to 33.4, and the liquid evaporates with the absorption of 330 cal. per g. of ammonia vaporized. This cycle of compression and evaporation is utilized in refrigeration.^ The liquid has a density of 0.677 at - 34, and a dielectric constant of 18.9 at 5 C. The specific conductivity at - 33 8 As a solvent for polar salts, is about 10~ reciprocal ohms.
192
REFERENCE
[Ch. XI
resembles water more closely than any other substance, although, due to the lower dielectricconstant, salt solutions
it
have a much lower activity (Append. IV). The remarkable ability of liquid ammonia to ionize the
alkali
metals to give a solution containing the "free" electron has been mentioned (cf. IV 2). The potential of 33 against a hydrogen electrode e N H,"~ = ^metai" couple at
is
given as about 1.90 volts.

salts
monium
in
liquid
The ammonia
solubilities of the
am-
For example, the values in grams for NH 4 NO 3 390, and NHJ, 369 at 25.
,
are remarkably large. 3 are per 100 grams of
NH
The
structure of the
ammonia molecule
is
a pyramid with
the nitrogen at the apex. The N-H distances are 1.016 A and the height of the pyramid 0.360 A. The dipole mo10~ 18 e.s.u. The nitrogen atom ment of the gas is 1.46
has two equally stable positions, one above the plane of the hydrogen atoms and the other below the plane and vibrates back and forth between these positions. The frequency of 10 10 per second and is the basic this cycle is 2.387013 time unit in the ammonia "atomic" clock. Liquid ammonia is sold under pressure in iron cylinders, and is the most convenient source of the gas. The greater part of the ammonia produced is absorbed in sulfuric acid
and
sold as fertilizer.
is
monia,
used in washing and cleaning.

are
v
Household ammonia, or aqua amLarge quantities of
ammonia
oxidized to nitric acid (Par. 32). The most important fields of consumption are given in Table IV.
now
TABLE
AMMONIA
Production
IV
IN U. S. 1948
TONS OF N2
232,000 1,090,000
Coke ovens
Synthetic
Consumption
Fertilizer
Manufacture
of
HNO
Aqua ammonia
Liquid, largely for refrigeration
Salts
860,000 270,000 50,000 30,000 30,000
11]
GROUP
V. NITROGEN,
PHOSPHORUS,
ETC.
193
Reactions of Ammonia. Ammonia does not react readily with air, but in pure oxygen it burns to water and = 2N 2 + 6H 2 O; 301 kcal. In the nitrogen: 4NH 3 + 3O 2 as a catalyst, the reaction goes to presence of platinum 50 2 = 4NO + 6H 2 O, 215 kcal. This nitric oxide: 4NH 3 selective oxidation is the basis for the commercial prepara11.
tion of nitric acid
from ammonia (Par.
32).
The gas
is
also
oxidized to nitrogen by passing over many heated oxides, The e.g. CuO, and by chlorine and bromine (Par. 22). oxidation of ammonia and ammonium ion in water soludiscussed in subsequent paragraphs. Ammonia reacts with water to form ammonium hydroxide (Par. 13). It is absorbed by many salts with the
tions
is
formation of ammoniated compounds similar to solid hyAmmonia forms drates, e.g., CaCl 2 -2NH 3 CaCl 2 -4NH 3 complex ions with solutions of many metal ions which possess pronounced "coordination" tendencies (cf. VII 2),
, .
e.g.,
Ag(NH
3) 2
TABLE V
ANALOGY OF WATER AND AMMONIA SYSTEMS
Ammonia shows acid properties, in that the three hydrogens are replaceable by metals as illustrated by the following: NaNH 2 sodium amide; Ag 2 NH, silver imide; Li 3 N, lithium nitride. These compounds are formed by heating the metals in ammonia gas: 2Na 2NH 3 = 2NaNH 2 2
,
+H
194
REFERENCE
[Ch. XI
The
acid ionization of
small,
ammonia, however, is extremely and even sodium amide is completely hydrolyzed
in water:
NaNH + 2H O = Na+ + OH~ + NH

2
2
OH.
The amides may be

12.
considered as the analogues of the hy-
droxides of water systems (Table V).
may
Many acids exist, both inorganic and organic, which be thought of as formed by the replacement of the
e.g.,
OH- by NHr, OH
O
2
NH
OS
2
O
CHa C
CHj C
OH
Sulfuric acid
NH
Sulfuryl
OH
Acetic acid
NH
Acetamide
amide
On the other hand, such adds may be considered as compounds in which one or more of the hydrogen atoms of ammonia is replaced by an acid radical, e.g.,
HSO
HSO
/ N H
H
Ammonia
/ N H
H
Amidosulfonic
acid
/ N HSO
H
HSO
/ N HSO
HS0
Imidosulfonic acid
Nitnlosulfonic acid
The compound
2 2 nitramide, results from the substitution of the nitro-group for one of the hydrogens of ammonia. It is a solid which melts at 72 with decomposi,
NH NO
tion.
The constant
into
H+ and
slowly
NHNO ~ is 2.55 X 10~ The acid solution The dedecomposes, NH NO = N O + H O.

7 2
.
for its dissociation in
aqueous solution
2
composition is rapid in alkaline solution. The compound is an isomer of hyponitrous acid. 13. Ammonium Hydroxide. Ammonia Is extremely soluble in water (1,300 vol. per vol. of and 700 vol. at 2 O at 4 OH. 20), forming solutions of ammonium hydroxide, + = The hydroxide is a weak base: 4 OH 4 OH~, 10~6 A IN solution thus contains 0.00427V KM* = 1.81
NH
NH NH +
14]
GROUP
.
V. NITROGEN,
PHOSPHORUS,
ETC.
195
for the weakness of ammonium hydroxassumed that a hydrogen atom acts as a bond as indicated by the formula:
ide, it is generally
OH
To account
H N H O H H
:
Values for the specific gravity of aqueous solutions of ammonia are given in Table VI.
TABLE
SPECIFIC GRAVITY OF
VI
15
AQUEOUS AMMONIA AT
C.
Water and ammonia react to form solid ammonium hy79. These pure com(NHUÔ, at so only the water solutions pounds decompose upon heating, of ammonium hydroxide are known at room temperature. The free ammonium radical, 14. Ammonium Amalgam. NH 4 may be prepared as an amalgam by the reduction of
droxide and the oxide,
,
ammonium ion in the presence of mercury: NH 4+ + e~ = NH 4 The reduction may be accomplished electrolytically, using a solution of ammonium sulfate and a mercury
.
cathode, or by the action of sodium amalgam upon an ammonium solution. At ordinary temperature, the radical is unstable, decomposing into ammonia and hydrogen, and the amalgam is a spongy mass, due to the bubbles of gas, but at low temperatures the amalgam is a hard, stable subIn forming an amalgam, the ammonium radical thus appears to possess distinctly metallic properties.
stance.
196
REFERENCE

Salts.
[Cfi.
XI
15.
Ammonium
its salts.
Ammonium
ion resembles thal-
lous
crystalline four hydrogen atoms are arranged in tetrahedral form about the nitrogen, and the approximate
and potassium ions
in the solubility
and
form of
The
diameter of the ion in crystals is 1.50 X 10~ 8 cm. Two points of dissimilarity from thallous and potassium ions are the weakness of ammonium hydroxide, and the volatility of
ammonium
salts.
All
ammonium
salts volatilize at
temperatures around 300, except compounds, such as the nitrate and dichromate, which decompose with the oxidation of the ammonia. The vapor of the sublimed salt is largely dissociated into ammonia and the acid, e.g. NH 4 C1
In fact, it is this dissociation taking place on the crystal surface which is probably responsible for the ready volatility of the salt. Ammonium salts are highly ionized, and slightly acid by hydrolysis.
(s)
3
NH
(gas)
HC1
(gas).
The constant
(NH
+ 4
), is
5.5
for the hydrolysis, 10~ 10 at 25 C.
A IN NH
= (NH OH)(H+)/
4
+ solution thus
contains 2.3
16.
10r*N H+.
chloride
is
Ammonium
made by absorbing ammonia

from solution
in feath-
in hydrochloric acid.
It crystallizes
ery crystals of the regular system, having the same type of crystal lattice as cesium chloride, but changing at higher temperatures into the sodium chloride lattice. The vapor
pressure of the solid reaches one atmosphere at 338
C.
The
salt is used "galvanizing" iron, clean metal surfaces of oxides, the action being due to the presence of free hydrochloric acid in the vapor. It is also
in
and
in soldering, to
used in "dry" batteries

ing.
(cf.
Its
common name
is sal
XVIII 9), and ammoniac.
in textile
dye-
Ammonium bromide and

ride.
iodide are similar to the chlo-
The
nitrate exists in five crystalline modifications be-
20 and 125. When heated tween the temperatures of gently, it decomposes into nitrous oxide and water. The
compound
is really
a high explosive, but
is
extremely
diffi-
17]
GROUP
V. NITROGEN,
PHOSPHORUS, ETC
197
cult to detonate.
However, disastrous explosions have ocemployed extensively as an explosive mixed with trinitrotoluene under the name of amatol.
curred.
17.
It is
Ammonium
and
lose
4
= NH + + HCO - + NH The so-called solid ammonium carbonate is a mixture of the bicarbonate and ammonium carbamate, and is made by heating a mixture of the ammonium sulfate and calcium carbonate in iron It may also be formed by the reaction of amretorts.
lyzed,
ammonia
carbonate solutions are highly hydroto form the bicarbonate: 2NH 4+

3
+ CO,"
3.
monia and carbon
dioxide.
:0
4
2NH + CO
3
equals
H N C O NH
2
or
H N
:
C O
:
NH
ii
Upon
urea:
heating,
4
2
NH CO NH
ammonium carbamate loses water = CO(NH 2 + H O.

2 )2
2
to form
Ammonium
ammonia
of
sulfate, prepared
by passing "by-product"
into sulfuric acid, has been the principal source
ammonium compounds. Synthetic ammonia has, however, now become the greatest potential source of ammonium compounds. The sulfate is employed extensively
as a fertilizer, but if a cheaper method of preparing phosphoric acid from phosphate rock can be developed, the sulfate will doubtless be replaced by the phosphate, as the
absorption of ammonia in this acid will serve to eliminate the cost of the sulfuric acid and at the same time give a compound, both constituents of which are valuable fertilizers.
Ammonium sulfide, (NH 4 )

solutions
2 S,
solutions,
made by
passing
hydrogen sulfide into ammonium hydroxide, are largely hydrolyzed to the bisulfide, NH 4 HS. The use of these
frequently referred to in connection with the precipitation of metal sulfides in qualitative analyses. The sulfide readily absorbs sulfur forming poly sulfides (cf.
is
198
REFERENCE
[Ch. XI
XI
26). The polysulfide also forms through the, action of the oxygen of the air upon solutions of the sulfide. Ammonium thiocyanate, 4 SCN, is used in dyeing to of iron salts upon the color (see prevent injurious action Fe(SCN)s). It is sometimes prepared by the reaction of
NH
ammonia and carbon
+H
2 S.
Ammonium
+ 2NH = NH SCN dithiocarbamate, NH S CNH forms

disulfide:
CS 2
2,
as an intermediate
compound.
peroxysulfate, (NH 4 )2S 2 8 formed by the of a concentrated solution of the acid sulfate, is electrolysis
,
Ammonium
an important oxidizing agent.
The perchlorate, cobaltinitrite, chloro18. Analytical. platinate, and acid tartrate, may be precipitated similarly to the potassium salts; but a more delicate test for ammonium compounds is the formation of ammonium hydroxide upon the addition of a strong base and the subsequent volatilization of ammonia gas: NH 4+ + OH~ = NH 4 OH and NH 4 OH = NH 3 + H 2 O. The ammonia is detected by its odor, or by its action upon moistened red litmus paper
placed over the solution. Quantitatively, ammonium salts are determined by treating the sample with excess sodium hydroxide, and distilling the ammonia into a known volume
of standard acid.
The excess acid is then titrated with standard base, using methyl orange as an indicator. Small amounts of ammonia are determined by means of Nessler's reagent (cf. VIII 25). 19, Hydrazine. Ammonium salts may be oxidized electrolytically to hydrazine, if certain viscous substances, such as glue or starch are added to the electrolyte. Hydrazine is usually prepared by treating dilute ammonia (in the presence of glue, etc.) with chlorine to form the monoand then adding an excess of am2 C1; chloramine, monia: 2NH 3 and 2NH 3 C1 2 - NH.C1 4 C1, = N2 4 C1. The sulfate, H 4 <H 2 SO 4 or 2 C1 4 2 (N 2 5 ) 2 SO 4 is not very soluble, and hydrazine is readily purified by crystallization as such. It may also be prepared
+ NH H
NH + H + NH
+ NH
20]
GROUP
V. NITROGEN,
PHOSPHORUS, ETC
199
of the potassium sulfite-nitric oxide com-2NO, with sodium amalgam, and by the reducplex, tion of a number of organic nitrogen compounds. With water hydrazine forms the weak base, N 2 H 5 OH, which For the dissociation, gives in acid solution the ion, N 2 H 5 N 2 H 4 + H 2 O = N 2 H 5+ + the value for is 8.5
by the reduction
K SO
2
"
".
10~7
The constant
for
NH H
-
OH",
6
K
.
is
8.9
10~ 16
The
pure substance may be prepared as a fuming liquid by 2 H 4H 2O distilling hydrazine hydrate with barium oxide:
BaO = N 2 H 4
Ba(OH)
2.
The
liquid boils at 113.5
without decomposition. Hydrazine is a good reducing agent even in acid solution. It is oxidized quantitatively to nitrogen by iodate, chlorine, bromine, and iodine. It is also oxidized by chloric acid with osmium salts as a catalyst.
The alkaline solution is readily oxidized by oxygen. Many oxidizing agents which gain one electron per molecule react with hydrazine to form both nitrogen and ammonia: N 2 H 5+ + Fe+++ = Fe++ + JN 2 + NH 4+ + H+. Hydrazine
reacts with nitrous acid to form hydrazoic acid (Par. 21). Hydrazine is not easily reduced to ammonia. It reacts
The rela2 3 readily with metallic sodium to form tion of hydrazine to ammonia is analogous to that of
.
NaN H
hydrogen peroxide to water. NH 2 OH, pre20. Hydroxylamine. Hydroxylamine, the reduction of 1 mole of nitrous acid with pared by 2 moles of sulfurous acid (Par. 30). The reduction is carried in neutral solution (NaHSO 3 ) and forms first the out at
ion of hydroxylaminedisulfonic acid
:
NO
2
"~
2
-f
SO
3
+ HSO
~~ 3
= NOH(SO3)
acid solution:
This
is
then hydrolyzed by heating in
NOH(SO
3) 2
+ 2H O = H NOH+ + H+
Hydroxylamine is also obtained by the reducand nitrous acid in dilute solution, by strong reducing agents such as tin, and zinc. The electrolytic reduction of nitric acid with most metal electrodes yields ammonia, but with a mercury cathode, hydroxylamine is formed. Hydroxylamine in solutions of acids forms the ion,
.
2SO 4
tion of nitric
200
REFERENCE
3 OH"*~,
[Ch. XI
NH
as
and upon evaporation

are obtained.
6.6
of the solution, salts such

2 2
NHaOH-Cl,
NH OH + H O = NH OH+
3
+ OH"~,
3
X
3
10~ 9
The anhydrous compound may
be prepared by
holic solution of
distilling,
under reduced pressure, an alcothe hydrochloride with sodium methylate;

2
3
NH OH'C1 + CH ONa - NH OH + CH OH + NaCL

The melting
22
point
is
33, and at 57, the vapor pressure
is
mm. At higher temperatures the liquid is very explosive. Ferric ion (in excess) in acid solution oxidizes hydroxylamine quantitatively to nitrous oxide, and more powerful
If
oxidizing agents give nitrate.

is in
the
H+
is
excess, nitrogen
is
largely formed.
low and NH 2 OH Hydroxylamine is
reduced by moderately powerful reducing agents. As indicated above, the hydrogen atom of hydroxylamine may be substituted by sulfonate groups. Although the resulting acids are unstable many of their salts are well-
known, e.g.,K[HONHSO 3 ], potassium hydroxylamine monosulfonate, and K 3 [SO 3 ON(SO 3 )2], potassium hydroxylamine trisulfonate. Both a di- and an isodisulfonate are known.
II
S0 3 H
HOjSON
SOsII
Hydroxylamine
isodisulfonate
HON
S0 3 H
Hydroxylamine
disulfonate
21.
mide at 200
in the cold
2 O. Hydrazine and its derivatives react with nitrous acid or trichlornitride to form The 3 + 2H 2 O. hydrazoic acid: N 2 H 4 + O 2 .NH = dissociation of hydrazoic acid is about like acetic acid 5 = 1.8 10"" and the ion, 3~, resembles chloride ion in the solubility of its salts and in its reversible reaction with hypochlorous acid: HC1O C1N 3 3 ^ 2 CX
= NaNs + H
Hydrazoic Acid. Nitrous oxide reacts with sodato form sodium azide: N 2 + HijNNa
:
HN
+ HN
+H
221
GROUP
V.
i01
The
product, chlorazide, like chlorine, is a gas, but is highly explosive. The iodo-azide also exists. Sodium azide
tastes like
free acid boils at
sodium chloride, and is highly poisonous. The 37, but the warm liquid is violently ex-
plosive, as the
The
acid
is
reducing agent.
volts
compound is highly endothermic (62 kcal.). both a powerful oxidizing agent and a powerful + + N2 = - 1.82 4 3 + 3H+ + 2e~,
NH
HN
and
HN
= |N 8 + H+ +
<r,
2.8 volts.
The
~
acid
3
reacts
quantitatively
with eerie ion:
" 2Ce~M H + 2HN
= 3N 2 + 2Ce+++ + 2H+.
azides are in line, with a distance between the atomic centers of 1.16 X 10~ 8 cm. Lead azide is now used extensively in the manufacture of percussion caps. 22. Halogen Nitrides. Trichlornitride, also called nitro-
The crystal structure of the from X-ray data show that the three nitrogen atoms
gen
trichloride, C1 3 N, is formed almost quantitatively by the action of excess chlorine or hypochlorous acid with am+ monium ion in excess of strong acid 4 3CU = C1 3 + = C1 3C1- and 4H+ 3HC1O H+
:
NH
+ + 3H
NH
N +
O.
With low concentration
of
hydrogen
the
ion, nitro-
gen
is
evolved,
probably through
leaction:
NC1 3
+ NH
3
+= 4
tions of
NH +
N 2 + 4H+ + 3C1-. With dilute equimolal soluammonia and hypochlorite, chloramine is formed: C1O~ = NH 2 C1 + OH~. Both substances are highly
explosive, oily liquids, and are partially hydrolyzed by water to ammonia and hypochlorous acid. Because of this
type of hydrolysis and the method of preparation, the nitro3 oxidation state gen is often considered as being in the but the classification is not very significant in view of the non-polar character of the bonds between the nitrogen and
chlorine.
:
Cl
Cl
:C1:
Trichlornitride
H N H
:
*
Cl
Chloramine
Iodine reacts with ammonia, forming a dark brown solid.
202
REFERENCE

.
[Ch.
XI
the so-called nitrogen triiodide, I 3 N-NH 3 \yhen dry, it with the slightest touch. It may also be prepared explodes by the addition of iodine chloride in concentrated hydrochloric acid to
an excess of concentrated ammonia.
The
4 IO, appears to be formation of ammonium hypoiodite, an intermediate step. Bromine reacts with ammonia to liberate nitrogen, and the reaction is frequently employed to remove bromine from a solution. Nitrogen trifluoride has been prepared by the electrolysis of anhydrous am-
NH
monium
fluoride,
NH HF
4
2.
It is fairly stable.
,
Sulfur nitride, S 4 N 4 may be 23. Nitrogen and Sulfur. prepared by the action of liquid ammonia upon sulfur, or by the action of ammonia on sulfur chloride in benzene. The compound is orange-red and may be sublimed under
reduced pressure at 100, but explodes at higher temperatures. It hydrolyzes in water to form ammonia, sulfurous, and thiosulfuric acids. When N 4 S 4 is heated with CS 2 a deep red oil, said to be N 2 S 5 is formed. The highly explosive compounds (Se 4 N 4 ) x and Te 3 N 4 have been prepared.
OXIDES AND ACIDS OF NITROGEN

24.
Nitrogen forms oxides,
dation states
ing to the
is
+
1,
to
5,
which it possesses the oxiinclusive, and acids correspondin
+3, and
5 states.
In addition, there
a nitrogen peroxide, and a peroxyacid, and the sodium salts of hydronitrous acid H 2 NO 2 and of nitrohydroxyhave been prepared but these are lamic acid, H 2 2 Electronic formulae are given relatively unimportant. below. These must not be interpreted as representing the actual position of the electrons, but simply as a representation of the total number of electrons and a distribution which appears to be in harmony with known facts relating to the various compounds. In molecules which do not have completed octets of electrons, there doubtless is resonance of electrons between atoms with completed octets and those with incomplete octets. The relative positions of
ONNO
25]
GROUP
V. NITROGEN,
PHOSPHORUS, ETC
203
the atoms in the molecule are known, in a majority of cases, from X-ray data on the solid crystals.
:N ::N
::
H:
:N ::N
:H
Nitrous oxide
(+
:
1)
Hyponitrous acid (-f 1)
N
:O:
..
::O
Nitric oxide
(+
2)
"N:O:N:
o \J
Nitrous anhydride
:6::N:6:H
3)
(+
Nitrous acid
(+
3)
O \j
N
:O
O \j N
:O
(+4)
:
:
O N
vy
:O
Nitrogen dioxide
:
Nitrogen tetroxide
(+
4)
:O :O "N :0 :N"
f\ \s
f\ \s
:O *N :6 :H *O* vy
:
Nitric anhydride (-f 5)
Nitric acid
(+
5)
Nitrous Oxide. Nitrous oxide is prepared comby the decomposition of ammonium nitrate = 2 O + 2H 2 O. The 4 NO 3 through gentle heating: must be carefully controlled, as overheating may reaction result in the explosive decomposition into nitrogen, oxygen, and water. The oxide is also a product of various other re26.
mercially
NH
actions, including:
O. The oxide is a colorless gas which may be by a pressure of 50 atmospheres at 20. The liquefied It is soluble to the extent of critical temperature is 35.
3
2
+ HN0 + NH + H
2
NH OH-NO N + N + H
3
2 2
=
0;
N O + 2H N H -HNO
2
O;
HN
2
NO
water at 20, and at low temperatures forms a hydrate, N 2 O-6H 2 O. Band spectra data on the gas
1.3 per vol. of
204
REFERENCE

in a line,
[Ch. Xi
show all three atoms of the molecule to be oxygen on one end.
with the
is negative, about the gas is unstable in respect to the 19.7 kcal. per mole; and decomposition into its elements. However, the rate of de-
The heat
of formation of nitrous oxide
composition is not appreciable at ordinary temperatures. A glowing splinter bursts into flame in nitrous oxide, and phosphorus and sulfur burn readily, nitrogen being liberated in the reaction. Strong oxidizing agents, such as oxidize nitrous oxide to nitric oxide. Metals permanganate, do not tarnish readily in nitrous oxide, and it does not combine with nitric oxide as does oxygen. The gas is employed extensively as an anaesthetic. Inhaled in small amounts, it often produces a type of hysteria, hence its common name
"laughing gas."
in
The pure
liquid oxide
is
put on the market
heavy
26.
steel containers.
Hyponitrous Acid. Hydroxylamine is oxidized by mercuric oxide or nitrous acid to hyponitrous acid 2NH 2 OH
:
H N O + 2Hg + 2H O; NH OH + HNO + = H N O + H O. The ion is also formed by the reduction

2HgO =
2
2 2
2 2
2 2
of nitrite with
sodium amalgam or
electrolytically with a
mercury cathode. The silver salt, Ag 2 2 O 2 is slightly soluble, and the free acid may be formed by treating the silver salt with an ether solution of hydrogen chloride. Upon evaporation of the ether, the acid is obtained as a
,
highly explosive solid. In water solution the acid slowly = 2O 2O 2 2 decomposes into nitrous oxide and water: + 2 O. The reaction is not reversible. The double formula
HN
is assigned from measurements of the molecular weight in various solvents. The following potentials relate hyponi-
trous
2
acid
2
to
nitrous
2
acid
+ H N O = 2HNO + 4H+ + 4<r, - 0.80 volt, 2NH OH+ = H N O + 6H+ + 4e~, - 0.44 volt. ionization constants of H N O are K\ = 9 X 10"
2
3 2 2
and hydroxylamine, 2H 2 O and
The
and
10-".
nitroxyl,
The compound,
NOH,
appears to be formed as
27]
GROUP
V.- NITROGEN,
PHOSPHORUS, ETC
205
an intermediate step in the oxidation of hydroxylamine or the reduction of nitrous acid. Under various conditions it may react to give 2 O or 2 2 O 2 or it may react with excess hydroxylamine to give nitrogen, 2 + = 2 + 2 O. By its reaction with excess of nitrous acid
HN
NH OH
NOH
nitric oxide may be formed. Sodium reacts with nitric oxide at low temperatures to form NaNO, which may be considered to be a salt of NOH. The sodium compound liberates
N O with
2
water.
27. Nitric Oxide.
Pure
nitric oxide is
formed by the
1
addition of dilute nitric acid

tion of ferrous sulfate
and
+ NO
some
(sp. gr. 1.2) to a boiling solu" " dilute sulfuric acid SFe" 4 4H+
:
= 3Fe+++ +
NO + 2H
O. It
may
also be
formed
by the reduction
such as copper or
of dilute nitric acid

silver,
by various metals, although usually contaminated by
nitrogen, nitrous oxide, or nitrogen dioxide. Nitric oxide is highly endothermic, but is the most stable
of the nitrogen oxides at high temperatures. It is formed to a small per cent in a mixture of nitrogen and oxygen in an
electric arc, the reaction being the basis for the various arc
processes for the fixation of nitrogen (see Nitric Acid). The oxide is also an intermediate step in another important
process for the manufacture of nitric acid, namely, the oxidation of ammonia (Par. 32).
Nitric oxide resembles nitrogen
properties.
The
critical
and oxygen in physical 93, and the temperature is

of dissociation into
boiling point
150.2.
The heat
and O 2 about
21 kcal., and into atomic nitrogen and oxygen 150 kcal. It is doubtless this latter large heat that renders the rate of decomposition so slow at low temperatures. The molecule contains an odd number of valence
is
electrons, but possesses only slightly the general tendency of such compounds to form double molecules, nor is it
colored.
In the liquid state, however, it appears to be The oxide is about 90 per cent associated into (NO) 2
.
magnetic,
its
magnetic susceptibility being approximately
206
REFERENCE
[Ch.
XI
half that of oxygen,

(cf.
which contains two unpaired electrons
s).
At ordinary temperatures, nitric oxide reacts with oxygen or air to form brown nitrogen dioxide but the equilibrium
;
is
reversed at higher temperatures (Table VII): 2NO C>2 wood or phosphorus con? 2NO 2 Vigorously burning
does not support the combustion of more feebly burning substances, such as sulfur or a tallow candle. The oxide is somewhat soluble in water, 4.7 vol. per 100 vol. of water at 20 and 1 atm. It is, however, very soluble in solutions of ferrous salts due to the formation of the dark brown colored complex ion, FeNO++ Complex ions with cupric, cobaltous, and (cf. Par. 39). also exist, as well as the complex sulfite, 2 SC>3 platinous
tinues to burn in nitric oxide, but
it
2NO.
sesquioxide,
Nitrogen Sesquioxide, and Di- or Tetra-oxide. The N 2 C>3, is the anhydride of nitrous acid: 2Os + H 2O = 2HNO 2 The acid is very unstable and readily evolves the oxide, or, more correctly, a mixture of nitric oxide and nitrogen dioxide, since the sesquioxide is itself unstable at ordinary temperatures: N 2 O 3 = NO + NO 2 The equimolal mixture of oxides may be condensed to a dark blue liquid boiling at 3.5. If the liquid is completely dried, it may be vaporized without dissociation.
28.
(also incorrectly called peroxide), is At the in the liquid to tetroxide, 2 4 largely polymerized
The
dioxide,
NO
NO
boiling point, 21.3, the gaseous tetroxide is only about 20 per cent dissociated into the dioxide, but at 135 the dis-
sociation
is
dissociate into nitric oxide
99 per cent. Above 150, the dioxide begins to and oxygen.
TABLE
VII
DISSOCIATION OF NITROGEN DIOXIDE
29]
GROUP
dioxide
is
V. NITROGEN,
PHOSPHORUS, ETC
like the
207
The
an "odd molecule," and
majority
of such molecules, in addition to its tendency to polymerize, it is colored, the color in this case being a deep red-brown.
The pure
tetroxide, however, is colorless, and therefore, undergoes a striking color change.
upon heating,
OVM40
'
2N0 2
Deep brown
'
2NO + O 2
Colorless
Colorless
These oxides are involved in three important equilibwith water, nitric, and nitrous acids: (1) In small concentrations, nitrogen dioxide reacts with water in the cold to give a blue solution of nitric and nitrous acids: 2NO 2 = 10 5 It follows from 2 + H+ + NO 3 -, + H 2O = the equilibrium constant that in a dilute solution of the two
29.
ria
HNO
acids the concentration of nitrogen dioxide is very small. (2) Nitrous acid is unstable in respect to the decomposition:
3HNO = H+ + NO
2
+ 2NO + H
O,
30.
This
equilibrium is comparatively and, from the value of the constant, is rather easily reversed. (3) In warm concentrated solutions of nitric acid, the quantity of nitrous acid, which may be present, is very
small,
2
slow in cold dilute solutions,
+ H O = 2NO
and the principal equilibrium is the following: 3NC>2 3 + 2H+ + NO, = 2 X 108 Although
the equilibrium constant favors largely the formation of nitric acid from the dioxide, concentrated nitric acid may, however, be reduced by nitric oxide. The third reaction is
extremely important in connection with synthetic nitric acid processes (Par. 32). With alkaline solutions only reaction (1) occurs, i.e. nitrate and nitrite are formed and the equimolal mixture of NO and NO 2 gives almost pure
nitrite.
It follows
from these equilibria that the concentration of
nitric acid affects greatly the reduction products of the acid. This concentration effect is illustrated by the following sum-
208
REFERENCE
[Ch.
XI
mary
of the products formed by the action of nitric acid arsenous oxide upon
:
SO. Nitrous
acid,
HNO
2
2,
Acid and Nitrites. The formation of nitrous from the dioxide or sesquioxide has been dissolution containing nitrous acid may also the hydrolysis in dilute acid of nitrosylsulfuric
3 2
cussed above.
be formed by
acid:
NO HSO + H O = 2H+ + SO ~ + HNO

4
2.
solution of nitrous acid
is
conveniently formed by the addi.
tion of sulfuric acid to a nitrite in the cold.
Nitrous acid is 4 The weak, the dissociation constant being 4.5 X 10~ solution has a slight bluish color. The decomposition of the water solution has been discussed (Par. 29). Nitrous acid is
a rapid and
fairly strong oxidizing
agent
cr,
NO + H O = H+ + HNO +
2 2
0.99 volt
thus oxidizes iodide quantitatively to iodine. Certain strong reducing agents, e.g., stannous ion, are able to reduce nitrous acid to the negative oxidation states, but with many equally strong reducing agents, e.g., titanous ion, In general, such reductions the reduction stops at NO. involve a number of steps, but only in the case of sulfurous acid has the mechanism been worked out.
It
HNO
acid
With
2
HSOr
With
HSO -
>HSO 8 -NO
Nitrososulfonic acid
With 3 >(HSO 3 ) 2 NOH

Hydroxylamine
disulfonic acid
HSOr
>(HSO 3 ) 3 N.
Aminetrisulfonic acid
Nitrous
With
With
With
H+
H+
HNO(H N
2
2)
H NOH
2
HN
3
Hvponitrous acid
Hydroxylamine
Ammonia
30]
GROUP
V. NITROGEN,
PHOSPHORUS,
ETC.
reactions indicated on the horizontal are reversed in strong alkali. The reduction products may be hydrolyzed in acid solution to form the compounds indicated by the vertical arrows. The reduction potential of nitrous acid to
The
ammonium ion is
2H 2 O + 70H- +
NH +
4
HNO +
2
2
7H+
6<r,
0.86 volt
/and in alkaline solution:
NH
2
NO - + SH O +
2
6e~,
+ 0.15 volt.
0.94 volt.
Nitrous acid
2
may
also act as a reducing agent:
HNO + H O
/\
is
= 3H+
+ NO
2e~,
strong oxidizing agent is thus required, but the reaction quantitative with permanganate. Nitrites are usually prepared by heating the alkali nitrates either alone, 2KNO 3 = 2KN0 2 2 or with carbon or lead, to decrease the temperature of conversion: 2KNOa
+ C = 2KNO + CO
2
2.
Nitrite forms
complex ions with many positive
ions, in-
cluding cobaltic, ferrous, chromic, cupric, platinous; the most important being that with cobaltic ion, Co(NO 2 )6 The alkali nitrites are extremely soluble, but the silver nitrite is
but slightly soluble. The

2
silver salt in contact
with
solution decomposes
tion:
upon heating, according to the equa-
2AgN0 = Ag + NO + Ag+ + NOr.
ammonia and with organic + primary amines to form nitrogen: NH 3 + HNO 2 (NH 4 + NO 2~) = N 2 + 2H 2 O; RNH 2 + HNO 2 = N 2 + ROH + H 2 O; CO(NH 2 ) 2 + 2HNO 2 = 2N 2 + CO 2 + 3H 2O. The reaction with urea, CO(NH 2 ) 2 is often employed to remove nitrites from solution. Nitrous acid forms nitrosoamines with secondary amines: R 2 NH + HNO 2 = R 2 N-NO
Nitrous acid reacts with
,
aniline hydrochloride in the cold, nitrous acid forms diazonium chloride: C 6 6 2 2 -HC1 = C 6 6 2 C1 2H 2 O. This reaction is important in the
2
+H
O.
With
H NH
+ HNO
HN
210
REFERENCE
[Ch.
XI
synthesis of many organic compounds. Due to the weakness of nitrous acid, soluble nitrites are slightly hydrolyzed. Nitrites are readily distinguished from nitrates by the fact
that ferrous ion is oxidized in dilute acid (acetic) by nitrite, but not by nitrate, to give (with excess of the ferrous ion) the characteristic brown color of the Fe(NO)"f+ ion. Nitrites are quite poisonous. 31. Nitric Acid. Pure nitric acid is a colorless liquid, 41.6, boiling point 86 under density 1.54, freezing point and 35 under pressure of 20 mm. atmospheric pressure,
The
decomposition :4HNO 3 = 4NO 2 + 2H 2 O + O 2 The speed of the decomposition is increased by higher temperature and by light. The acid fumes strongly in moist air; the water solution has a constant boiling mixture of 68 per cent acid, density 1.41, and boiling point of 120.5. Upon repeated distillation of the pure acid, the constant boiling mixture is obtained through the formation of water by the decomposi.
concentrated acid is usually colored yellow, due to the presence of a percentage of the dioxide formed by the slow
tion reaction.
The anhydride
or pentoxide
may be formed by the

.
action
upon concentrated nitric acid: 2HNO 8 + P 2 O 5 = 2O 6 + 2HPO 3 It is a white solid which readily sublimes, and is easily decomposed into the dioxide and oxygen. The freezing point composition curves for the
of phosphorus pentoxide
and water show the existence of mono-, di-, and trihydrates at low temperatures. Water solutions of nitric
acid
acid are highly ionized (Append. IV).

32.
Three processes
for the
manufacture of
nitric acid
are
in use: (1) the older process of preparation from Chile saltpeter and sulfuric acid, (2) from nitric oxide
now
formed by the oxidation of ammonia, (3) from nitric oxide formed by the direct union of the elements. For many years, Chile saltpeter (cf. IV 23) was practically the
only source of nitric acid. The acid is produced from the salt by heating with concentrated sulfuric acid
33]
GROUP
V. NITROGEN,
PHOSPHORUS, ETC
.
211
The reaction pro3 2 4 3 4 ceeds because of the greater volatility of nitric acid, and is carried out under reduced pressure in order to operate at the lowest possible temperature, and thus keep down the decomposition of the acid. The reaction mixture is heated
in iron retorts,
NaNO + H SO = HNO + NaHSO
and
nitric acid
condensed and collected in
glass tubes and vessels. The sodium acid sulfate is valuable because of its acid properties, and is used in various industries.
it is now possible to make ammonia synthetically as low a cost per pound of nitrogen as Chile nitrate can at be mined and extracted, ammonia has become the principal commercial source of the acid. In 1938 the production of
Since
United States was approximately 160,000 from ammonia and only 20,000 tons from nitre. The tons oxidation is carried out by passing a mixture of ammonia (about 10 per cent) and air over a heated platinum gauze:
nitric acid in the
4NH + 5O = 4NO + 6H
3
O.
maintained at a temperature of mixture is heated to about 300 before entering the catalyst, and the heat of oxidation is sufficient to maintain the catalyst at the high temperature once the reaction is started. The efficiency of oxidation is about 96 per cent of the ammonia. The gas from the catalyst passes into absorption towers: 2NO + O 2 = 2NO 2 and 3NO 2 + H 2 O = 2HNO 3 + NO. The first of these reactions is rather slow, but is catalyzed by most surfaces. The second reaction has been
discussed at length under the oxide. The final two or three per cent of the oxide is absorbed in sodium carbonate solution to give a mixture of nitrate and nitrite. An important factor in the successful development of the process has been the use of chrome-steel alloys in the absorption towers, as
practically unattacked by nitric acid. 33. Synthesis of nitric acid from its elements can only be carried out at extremely high temperatures as indicated in
this
is
The platinum gauze is 900-1000 C. The gaseous
metal
Table VIII.
212
REFERENCE

TABLE
VIII
[Ch. XI
EQUILIBRIUM IN THE REACTION
N +O
2
2NO
existence of nitric oxide at ordinary temperatures is obviously due to a very slow rate of decomposition, and
this rate
The
becomes rapid only at high temperatures.
TABLE IX
ESTIMATED TIME REQUIRED FOR HALF DECOMPOSITION OF
NO
process for the direct synthesis of nitric oxide must, then, involve the heating of a mixture of oxygen and nitro-
gen to about 2000

(chiefly in
tric arc.
C., followed
by the rapid cooling
of the
equilibrium mixture.
This
is
carried out commercially

elec-
Norway) by blowing the gases through an
rapidly Under the best working conditions, the yield of nitric oxide is only about 2.5 per cent: it is difficult for the process to
The gases pass through the arc and are cooled by coming in contact with the walls of the tube.
compete with
from ammonia. Recently a somewhat simpler process has been developed in which a temperature of 2100 is reached in a MgO pebble bed by burning a mixture of gas and air. The hot gases are quickly cooled by mixing with more gas and passing through a second pebble bed. The air flow is then reversed and the cycle repeated. NO concentrations of about one per cent are obtained. In nature fixation of nitrogen during thunder storms is doubtless very large. 34. Nitric Acid as an Oxidizing Agent. The conditions for the reduction of nitric acid to NO, NOa~, or NO2 have
nitric acid
34]
GROUP
V. NITROGEN,
PHOSPHORUS, ETC
213
been discussed (Par. 29). The further reduction to 3 with SO 2 has also been treated (Par. 30) and this step may be carried out with Zn and other powerful reducing agents. The values for a number of the oxidation-reduction potentials at molal concentration are given below, but it must be pointed out that in the majority of the reactions the rates are slow, and that the speed becomes a factor of equal importance with the energy in determining what reactions
will occur.
NH
TABLE X
OXIDATION- REDUCTION POTENTIALS OF
Acidic solution
HNO
AND
NO ~
8
VOLTS as
8
2
H + N0 = N0 - + 2H+ + er H O + HNO - N0 - + 3H+ + 2~ 2H O + NO = NO ~ + 4H+ + 3<r 5H O + N O = 2NO ~ + 10H+ + Se~

2 2 2
2 2
3H O 2H 2 6H 2
3HiO
+ JN = NOr + 6H+ + Ser + NH OH+ - N0 - + 8H+ + 6e~ + N H ++ - 2NOr + 17H+ + 14<r + NH = NOr + 10H+ + Se~
2
3
0.81 0.94
0.96
1.11
1.24 0.73 0.84 0.87
The
potentials for the oxidation of

:
ammonia by
steps in
both acidic and basic solutions are shown
in the following
scheme
Acidic solution:
1.24
1.46
1.87
1.77
NH +
4
NH
2
+
o.99
NH OH+
3
N
-
1.59
1.07
0.81
NO
2
NO
0.10
HNO
0.74
NO
2
N(V
0.94
Basic solution:
3.04
NH OH
4
NH
2
NH OH
2
N
NO
2 4
0.76
0.46
NO
2
NO
NO 2
0.88
0.8S
NO ~
3
appears to give seldom realized, and then usually through the formation, first, of a compound of
Although the reduction to
free nitrogen
the greatest potential, this reaction is
214
REFERENCE
[Ch.
XI
nitrogen of negative oxidation number which reacts with nitrogen compounds of the same positive oxidation number,
e.g.
NH + + NOr = N + H O and NH OH + NOH N + 2H O (Par. 26). The values in the table show
4
that nitrate in alkaline solution is not a powerful oxidizing agent. The values in the table apply to molal concentrations and cannot be used to predict the action of
concentrated nitric acid, which
is
a far more powerful
Nitric acid is reoxidizing agent, especially duced by sulfurous acid or acid sulfites through the forma= NOtion of nitrosylsulfuric acid, 2 2 SO 3
when
heated.
HONO + H
+
O, and its subsequent hydrolysis in dilute acid. 35. Nitric acid reacts with chloride ion according to the 3C1~ = NOC1 2H 2O. C1 2 equation 4H+ +
4 2
:
HSO + H
NOr +
is
The compound, NOC1,
nitrosyl chloride, a liquid boiling

it
at 5.6, and upon heating, into nitric oxide and chlorine.
very readily decomposes

of nitric
The mixture
is
and
hydrochloric acids, solving gold and platinum, which acid alone. This, however, is not due to an increase in the oxidizing potential of the nitric acid in the presence of the chloride, but rather to an increase in the reduction potential
of these metals in the presence of the chloride (cf. VII 31). Fluorine reacts with nitric acid to form gaseous fluorine
known
as aqua regia,
capable of diswill not dissolve in nitric
The fluorine is bonded to an oxygen. 3 F. nitrate, 36. Nitric acid reacts with organic hydroxides to
nitrates, for
3
NO
form
example with glycerine to form "nitroglyc3 3 3 6 3 ) 3 + 3H 2 O, and with hydrocarbons, such as benzene, to form nitro comerine,"
C H (OH) + 3HN0 = C H (N0

5
pounds such* as nitrobenzene: C 6 H 6 + HNO 3 = C6 H 6 NO 2 + H 2 O. In both of these reactions, water is produced, so

that the reaction
is
favored by the presence of concentrated
sulfuric acid to lower the activity of this product. Large quantities of the mixed concentrated acids are manufac-
tured for this purpose. At present, the major portion of the

nitric acid
manufactured
is
consumed
in
some form
of
38]
GROUP
V.
215
organic nitrate or nitro-compound, the more important being the explosives, plastics, varnishes, and dyes (cf.
XHI
nitrates of the metals are, in general, readily soluble in water. The nitrate group shows but slight tendencies to form coordination compounds. The alkali
29). 37. Nitrates.
The
nitrates
= 2NaNO 2 + O
decompose upon heating to form nitrites: 2NaNOa The nitrates of the more noble metals 2
.
form the dioxide,
e.g.
2Cu(NO 3 ) 2 = 2CuO + 4NO
+O
2.
Ammonium
water:
nitrate
decomposes into nitrous oxide and
= N 2O + 2H 2 O. 4 3 data on the crystalline nitrates show that the three X-ray oxygen atoms are arranged symmetrically about the nitrogen atom in the same plane. The properties of many nitrates have been discussed under the various positive constituents, the more important
being the salts of sodium, potassium, ammonia, and calcium. Formerly the largest use of a nitrate was in the manufacture of gunpowder, consisting of potassium nitrate, 75 per cent; charcoal, 15 per cent; and sulfur 10 per cent. This mixture is moistened, ground, and the dried product granulated. When ignited, the powder burns and liberates a large volume of gases consisting mainly of nitrogen, carbon dioxide, carbon monoxide, and some sulfur dioxide. This type of powder is not smokeless, since solid particles of potassium sulfide and oxide are dispersed in the gas
phase.
38.
NH NO
Peroxynitrogen Compounds.
to unite with oxygen at low temperature
Nitric oxide appears 180) to form (
the peroxide, NOs, which decomposes upon heating. The silver salt of the peroxynitric acid, HMO*, is said to be formed by the electrolysis of a concentrated solution of silver nitrate, but neither the free acid nor other salts have been prepared. The highly unstable acid, 4l is formed by the action of hydrogen peroxide upon nitrogen pentox-
HNO
ide:
H O + N O - HNO + HNO
2
2
8.
216
REFERENCE
[Ch. XI
The test may be carried brown complex ion, Fe(NO)"H out by the addition of about 5 cc. of ferrous sulfate solution to a few cc. of unknown solution. Holding the tube in an
".
The ferrous sulfate test for nitrates dethe reduction of nitrates by ferrous ion in conpends upon centrated hydrogen ion solution and the formation of the
39. Analytical.
inclined position, 36N H2SO4 is carefully poured down the brown side of the tube so that the two liquids do not mix.
ring at the junction of the
The
test is
liquids indicates nitrate. not satisfactory in the presence of chlorate, io-
two
dine, bromine, nitrite, ferrocyanide, or ferricyanide. The diphenylamine test for nitrates consists of the addition of a
solution of (C6 5 )2NH in sulfuric acid to 2 or 3 cc. of unknown solution on a watch glass. Upon gentle heating, a blue color is produced if a nitrate is present.
quantitative determination of nitrate is usually by reduction to ammonia and the determination as such, or the reduction to nitric oxide, and its
carried out either
The
estimation as a gas (nitrometer method). In the former process, aluminum or Devarda's alloy (Al 45, Cu 50, Zn 5) in alkaline solution is used as the reducing agent. The
ammonia
and
into excess standardized sulfuric acid, the excess of acid titrated with sodium hydroxide. The
is distilled
nitrometer process depends upon
the
2
reaction:
2
2NC>3"~
+ 8H+ +
The
3SO 4
+ 6Hg = 3Hg SO + 4H O +
4
2NO.
a gas burette or nitrometer and the quantity of nitrate calculated from the volume of gas. The base diphenylendoanilohydrotriazole, C 2 oHi 6 N 4 called nitron, forms a slightly soluble nitrate, C 2 oHi 6 4 HNOs, and this reagent can be used for the quantitative separation and estimation of nitric acid.
nitric oxide is collected in
,
PHOSPHORUS, ARSENIC, ANTIMONY,

40.
AND
BISMUTH
The elements
esting series in
group form an especially interthat they involve a complete transition from

of this
41]
GROUP
V. NITROGEN,
PHOSPHORUS,
ETC.
217
non-metallic to metallic character in both physical and chemical properties. It is, however, noteworthy that this transition is by no means uniform, but that there is rather an alternation in properties. Thus, nitrogen, arsenic, and bismuth form no pentachlorides, while phosphorus and
antimony do.
Figure 1 illustrates this alternation for the heats of formation of the trioxides and trichlorides when plotted against atomic numbers. This alternation extends to neighboring groups, as
illustrated
first
by
figures
|
|
50
for the heats of formation
40 so
20
10
of the dioxides of Group VI and second, in Group VII, | by the stability of oxides
of chlorine
.
20
40
60
80
Atomic Number but FlG 1 Heats of formation m kcal. per / not Of fluorine or bromine. equivalent against atomic numbers. Various other evidences of alternation may be discovered, such as the enhanced tendency towards hydration of the oxides of phosphorus and antimony as compared with those of their immediate
and
iodine,
'
neighbors.
Occurrence. Phosphorus is the only member of the group which is never found free in nature. It occurs principally as calcium phosphate, Ca 3 (PO 4 )2, and as apatite, Ca 6 F(PO 4 )3 and Ca 5 Cl(PO4 )3. The first of these is found in large deposits of phosphate rock in Florida, Tennessee, Montana, and neighboring states, and in northern Africa. It is the principal mineral constituent of bones and teeth, and bone ash is largely calcium phosphate. Apatite occurs
41.
in
many
rocks,
Canada.
Many
and important deposits are located in plant and animal tissues contain phos-
phoproteins, complex compounds of protein with phosphoric acid derivatives, such as casein in milk, and vitellin in eggs. The average human body daily excretes phosphorus com-
pounds containing about 2 g. of the element. Arsenic and antimony are occasionally found
free,
and
218
REFERENCE
is
[Ch.
Xt
bismuth
generally so found.
erals are the sulfides: arsenical pyrite,
Their most important minFeAsS; orpiment,

;
As 2 S 3
Oxides
;
As 2 O 3 senarmontite, Sb 2O 3 and bismite, Bi 2O 3 -H 2 O, and less frequently selenides and tellurides. Arsenides, such as FeAs 2 CoAs 2 and NiAs are not infrequent, and arsenic is a common impurity in sulfuric acid made from pyrites, in pig iron, and in commercial zinc. The most extensive deposits of antimony are located in China. The average percentage of the metals in the igneous rocks is given as: arsenic, 10"6 antimony 10~"7 and bismuth 10~ 8 The more important 42. Properties of the Elements. constants are summarized in Table XI. Like the physical corresponding elements of Group VI, phosphorus, arsenic, and antimony exist in a number of crystalline modifications. Phosphorus has the two familiar forms known as "white" and "red." The white modification is formed by
;
realgar, As 2 S 2 stibnite, Sb 2 S 3 also occur such as claudetite,

;
bismuthinite, Bi 2 S 3 .
rapidly cooling phosphorus vapor. It is a wax-like substance, of low melting point, very low heat of fusion (157 cal. per g. atom), high volatility even at room temperature
i
^
*
|
E
4000
3000 2000
1000
(Fig. 2) and is readily soluble in carbon disulfide (90 g.
per 100
g. sol.
at 10).
It
ignites spontaneously in air
and
200 300
is,
therefore,
usually
400
500
kept and worked underwater in which it is only very

000)
.
extremely poisonbeing a fatal dose, and the continued consumption of small amounts leads to chronic poisoning, one of the symptoms of which is necrosis of the jaw. The white is a metastable form and upon heating or exous,
It is
about 0.1
g.
posure to sunlight turns yellow and then red. The transition is catalyzed by iodine: a trace of the latter causes a
42]
GROUP
V. NITROGEN,
PHOSPHORUS, ETC
219
is
very rapid reaction at 200. The heat of the transition
3,700cal. The red modification does not have definite density or melting point and appears to be a transition form or mixture of the white and the real stable modification, violet phosphorus. The latter is difficult to prepare pure, but
be obtained by crystallization from a solution in molten lead. The properties of red phosphorus are essentially those of the violet. It is much less volatile than the white and is not appreciably soluble in carbon disulfide or other solvents. Red phosphorus sublimes without melting, unless heated under pressure, and from the shape of the vapor pressure curves there does not appear to be a transi-
may
is
two modifications. Red phosphorus not especially reactive, only slightly poisonous, and does not ignite below 240. White phosphorus has a molecular weight corresponding to p4 in its solutions and in the vapor state, but the red or violet is not sufficiently soluble to enable its molecular weight to be determined. Above 1,500, the vapor is somewhat dissociated into P 2 A third solid modification, black phosphorus, is formed when a pressure of 4,000 atmospheres is applied to the element at 200. Arsenic exists in a reactive metastable crystalline modification, the so-called "yellow" arsenic, and a grey semimetallic form. Yellow arsenic is formed by passing the vapor into cold carbon disulfide. The rate of transition into the grey form is rapid even at low temperature and instantaneous at room temperature in the sunlight. Yellow
tion point between the
.
readily, is extremely poisonous and Its molecular in air at room temperature. phosphoresces As4 The metallic form weight in solution corresponds to
arsenic
volatilizes
is steel is
grey in color with a bright luster, very brittle, and a good conductor of heat but a rather poor electrical conductor. It sublimes without melting unless heated under
pressure.
Antimony occurs
in modifications similar to
those of
220
arsenic.
REFERENCE
[Ch.
XI
Yellow antimony is transformed so rapidly into the it can be kept only at low temperature. also forms a metastable metallic modification Antimony known as explosive antimony from the character of its transition into the stable form when struck or scratched The reaction evolves 20 cal. of heat per gram. Yellow antimony is formed by the action of oxygen upon liquid stibine, SbH 3 at 90, and the explosive form by the electrolysis
stable form that
.
,
antimony trichloride. The form always contains some trichloride, and is explosive probably a solid solution of the chloride in yellow antimony.
of a concentrated solution of
The
stable modification
is
ing substance. It
is a silvery white, metallic appearextremely brittle and much less volatile
than arsenic.
Bismuth
form.
brittle,
one crystalline metallic It is grey white with a slight red tinge, hard and a very poor conductor of heat, and, although its
is
known only
in the
melting point is low, the boiling point is high. 43. Preparation of the Elements. Phosphorus is generally prepared from calcium phosphate through the reaction,
Ca 3 (PO 4 ) 2
is
+ 2SiO + 5C =
2
Ca 3 Si 2 O 7
+ SCO + P
2,
which
carried out at high temperatures, usually in an electric arc furnace. Phosphorus vapor leaves the furnace
along with the carbon monoxide and is condensed under water, while the calcium silicate is drawn off as liquid slag. The element was first prepared by Brandt in 1669, by the
destructive distillation of the solid residue from the evaporation of urine.
Arsenic, antimony, and bismuth may be obtained reduction of the oxides with carbon, e.g., As 2 O 3 + 3C
by the = 2 As
In case the ore is a sulfide, it to the oxide: 2As 2 S 3 9O 2 = 2As 2 O 3
+ 3CO.
may
first
;
be roasted
be used as the reducing agent: Sb 2 S 3 + 3Fe = + Native bismuth is easily extracted by taking advantage of its low melting point, and simply heating the ore and running off the metal. Most of the bismuth is obtained as a
6SO 2
or iron may 3FeS. 2Sb
44]
GROUP
V. NITROGEN,
PHOSPHORUS, ETC
221
by-product of copper, lead, gold, and silver from the flue dust of the smelters.
ores, generally
TABLE XI ATOM AND PHYSICAL PROPERTIES OF PHOSPHORUS, ARSENIC, ANTIMONY,

AND BISMUTH
tric
Commercial Applications of the Elements. The elecfurnace production of phosphorus has increased rapidly since 1937. The element is shipped in tank cars and most of it is later burned to P 4 Oi and made into various phos44.
large amount of the phosphorus is consumed in phates. the preparation of the sulfide, P4 S 3 (Par. 62), for use in
matches.
Formerly matches were made by dipping wood
lead splints into a paste containing white phosphorus, Due to its poisonous dioxide, powdered glass, and glue. nature, the use of white phosphorus is now prohibited in most countries and in its place the trisulfide is substituted.
When struck, the friction raises the temperature to the point

where the phosphorus
sulfide is rapidly oxidized
by the
S22
REFERENCE
fCh. XI
lead dioxide
and the match bursts into flame.
In the so-
called "bird's eye" match, the phosphorus sulfide is present only in the small tip. The safety matches now used so ex-
no phosphorus in the match head, but the coated with a mixture of red phosphorus, glue, and abrasive. The match contains a mixture of good oxidizing agents, such as potassium chlorate or chromate or lead
tensively contain
is
box
dioxide,
and reducing agents, as antimony
sulfide.
It
may
be ignited by striking on some surface of low heat conductivity, such as glass, and more readily on the surface of the box, since a trace of the red phosphorus is ignited by the
friction
and the heat kindles the match head.
Phosphorus is used in tracer bullets, and burning phosphorus is employed for the preparation of smoke screens. Ground with flour and grease, white phosphorus is used as a poison for rodents. Very little free arsenic is consumed. The annual consumption in the United States is around 100 tons. A small amount of element (0.5 per cent) is usually added to lead in making shot to harden it and also to increase the surface
The latter aids in obtaining perfect spheres when made by allowing molten drops to fall from a The use of arsenic as a metal-tempering material is height. increasing. Arsenical copper alloys are now employed in
tension.
the shot
is
products which require soldering, as their annealing temperature is high and the substance does not suffer loss of strength during heating. The trioxide is an important commercial compound. Antimony is a cheap metal which can be used in certain instances as a substitute for more expensive metals. Most of the world's supply comes from China. The annual consumption in the United States is about 20,000 tons. Its principal use is in the manufacture of alloys, especially those of lead and tin, the most important being type metal, white metal, hard metal, britannia, babbitt, and antifriction metal (see Alloys of Lead and Tin). The presence of
45]
GROUP
V. NITROGEN,
PHOSPHORUS,
of the metal
ETC.
antimony adds to the hardness
and also con-
tributes the property of expanding upon solidification, which makes these alloys very useful in the preparation of sharp castings. About half of the American consumption
goes into a lead alloy for battery plates.
Bismuth alloys also expand upon cooling and make good castings. A number of bismuth alloys can be prepared which melt below the boiling point of water, e.g.
Alloys of this type are used in automatic fire extinguishers which depend upon plugs of the alloy melting and releasing
water sprinklers, closing fire-doors, etc. Such alloys are also employed in safety plugs in steam boilers to guard
against over-heating. An alloy of 55.5 per cent Bi and 44.5 per cent Pb is utilized as a master pattern metal in the
foundry industry.
Pb, 0.5; Bi, 0.5)
for
An aluminum
is free,
cutting and
alloy (Al, 93.5; Cu, 5.5; is used as the material
aluminum
screws.
45. Reactions of the Elements. The reactions of phosphorus are markedly different for the two modifications. Yellow phosphorus in moist air at ordinary temperature emits a pale greenish light and gives off white fumes of the sesquioxide, and the reaction is accompanied by the formation of ozone. The light is not true temperature radiation but results from the conversion of some of the reaction
energy directly into light (chemiluminescence). The glow appears to be connected with the formation of trioxide and does not occur if the partial pressure of the oxygen is considerably increased, although oxidation to the pentoxide then takes place. Yellow phosphorus ignites at about 45, the red at about 260. The yellow modification likewise
824
REFERENCE
[Ch.
XI
ignites spontaneously in chlorine, but the red must be heated to start the reaction. Yellow phosphorus is also
soluble in hot alkalies liberating phosphine while the red is not although the energy of the reaction is favorable. Phos-
phorus reacts with sulfur forming sulfides and with the halogens (Par. 61). Moderately strong oxidizing agents oxidize phosphorus to phosphoric acid P + 4H 2 O = H 3 PO4 + 5H+ + Se~\ + 0.3 volt. The potential value indicates that even hydrogen ion should be capable of oxidizing the element but the oxidation appears to be slow with all weak oxidizing
;
agents. Arsenic, antimony,
oxide in
(Sb also
directly
and bismuth form surface films of moist air, and burn to the trioxide when heated forms some Sb 2 O 4 ). Like phosphorus, they unite
sulfur (Par. 62), the halogens
when heated with
(Par. 61), and various metals (Par. 63). The oxidation of the elements to the + 5 state becomes increasingly difficult
with increasing atomic weight. Concentrated nitric acid, acting upon the elements, forms H 3 AsO4 Sb 2 O 6 and Bi(NOa)3. The reactions are summarized in Table XII.
, ,
TABLE
XII
4G 2G
2G
REACTIONS OF PHOSPHORUS, ARSENIC, ANTIMONY, AND BISMUTH (G a any element of the group) - 2G 2O 5 See also P 2 O 6 and Sb 2 O 4 + 3O 2
+ 3X - 2GX
2
nM
+ 3S = G S
2
X = halide. GX etc.
6>
See also Par. 61 for
-f"
niG
Gm
See Par. 62 for other sulfides Formation of metal phosphides,

arsenides, antimonides,
and
bis-
muthides
Hydrogen Compounds. Gaseous hydrogen compounds the analogues of ammonia, are formed by all members of the group: phosphine, PH 3 arsine, AsHs; stibine, SbH 3 bismuthine, BiH 3 They are frequently referred to as hydrides, but since the hydrogen is undoubtedly more posi46.
;
; .
tive,
the
name does not appear
to be appropriate.
47]
GROUP
V.
NITROGEN, PHOSPHORUS,
ETC.
225
TABLE
XIII
PHYSICAL PROPERTIES OF HYDROGEN COMPOUNDS
47. Unlike ammonia, the other members of the group cannot be prepared by the direct union of the element and hydrogen. Phosphine decomposes readily upon heating; stibine decomposes explosively, and the bismuth compound is so unstable that a quantity of the gas is 80 per cent decomposed in 50 minutes at room temperature. The decompositioii of arsine and stibine is further considered under
the
test (Par. 64). method of preparation is the hydrolysis of a metal compound similar to the hydrolysis of magbinary 6H 2 = 3Canesium nitride to form ammonia: Ca 3 P 2
Marsh
general
Na As + 3H 2O = 3NaOH + AsH (OH) 2 + 2PH Zn Sb 2 + 6H 2 O = 3Zn(OH) 2 + 2SbH Mg Bi 2 + 6H 2 O = 3Mg(OH) 2 + 2BiH 3 Phosphine may also be prepared by boiling white phosphorus with a solution of an alkali: 4P + 3OH~ + SHaO = 3H PO - + PH There are usually present in the gas traces of the compounds ?2H 4 and P4 H 2 Arsine may be formed by cathodic reduction, or by the
3
;
3.
reduction of arsenic compounds in acid solution by zinc or
magnesium:
AsO 3
3Zn
+ 6H+ = AsH +
3
3Zn++
This reduction gives, of course, a mixture of the 2 O. gas and hydrogen. The same method is also applicable to the preparation of stibine, but the more powerful reducing agent, magnesium, must be used for bismuthine.
+ 3H
These compounds are all extremely poisonous and it is dangerous to inhale even small amounts. Because of the
226
REFERENCE
[Ch. XI
presence of arsenic in many acids and metals, arsine is a impurity in hydrogen prepared through their interaction, and such hydrogen should, therefore, not be inhaled unless it has been passed through permanganate
common
solution.
Phosphine ignites spontaneously in air. The gas burns to phosphoric acid: PH 3 + 2O 2 = H 3 PO4 If bubbled through water into air, the bubbles ignite at the surface and form beautiful smoke rings. Arsine and stibine readily burn in
.
air,
forming the trioxides.

is
If,
however, a piece of cold porce,
lain
The
phosphine and a hydrogen phosphide, P 4 H 2 or possibly P 12 H 6 which is a solid: 5P 2 H 4 = 6PH 3 + P4 H 2 48. Unlike ammonia, these compounds are only slightly soluble in water (PH 3 11 vol. in 100 vol. water at 15), and the solutions are not alkaline. The basic nature of the compounds decreases with the increasing size of the elements. Indeed, phosphine is the only one which resembles ammonia in the formation of salts, the phosphonium compounds, and these are far less stable than the ammonium
,
placed in the flame, it is coated with the free element. liquid compound, P 2 4 decomposes in the light into
compounds. Phosphonium
3
iodide,
PHJ,
is
formed by the reaction:

in
PH + HI = PHJ.
It
crystallizes
beautiful,
large,
highly refracting, square, prisms which sublime at 62. It is a powerful reducing agent, and is decomposed by water with the liberation of phosphine. Phosphonium bromide resembles the iodide, but the chloride can only be formed at room temperature under pressure (at 14 the dissociation = PH 3 + HC1, is about 20 atmospheres). pressure, PH 4 C1 Phosphine reacts with solutions of certain metallic ions, e.g. Cu++, with the formation of slightly soluble metal phosphides, which usually are of uncertain composition. Arsine passed into a solution of silver nitrate gives metallic silver and arsenious acid: AsH 8 + 6Ag+ + 3H 2 O = 6Ag + H 8AsO 3 + 6H+. Under the same conditions, stibine
50]
GROUP
V. NITROGEN,
PHOSPHORUS, ETC
227
gives silver antimonide:
3 3 Sb. Arsenic forms no compounds analogous to hydrazine but organic derivatives are known, such as As2(CH3) 4 cacodyl.
,
SbH + 3Ag+ = 3H+ + Ag
OXIDES AND ACIDS

49.
The
oxides and acids are summarized in Table
XIV.
TABLE XIV
ACIDS AND OXIDES OF PHOSPHORUS, ARSENIC, ANTIMONY, AND BISMUTH
Peroxyacids of phosphorus, H 4 P 2 O 8 and H 3 PO 5 also exist. The pentoxides, with the exception of that of phosphorus, readily evolve oxygen upon heating, forming the sesquiox,
ides.
ments
These oxides are formed also upon burning the elein air. Measurements of gas density show that the
sesquioxides, generally called the trioxides, are associated into double molecules, 4 O6 Phosphorus pentoxide has an enormous affinity for water, even removing it from con-
centrated sulfuric acid. The oxides of arsenic react slowly with water, while the oxides of antimony and bismuth show almost no such reaction. With increasing size of the atoms, the oxides become less acidic.
50.
Oxides and Acids of Phosphorus. The sesquioxide, of phosphorus ), is produced by the combustion
228
REFERENCE
[Ch.
XI
supply of air. It dissolves slowly in cold water, to form phosphorous acid, and violently in hot water, to form phosphoric acid and phosphine: 2P 2 O 3 + 6H 2O = PH 3 4- 3H 3 PO4 When heated in a sealed tube, it dein a limited
.
composes into the tetraoxide and phosphorus: 4P2Oa
= 3P 2 O4 +
2P.
The
trioxide
is
read-
ily
separated from the pentoxide by
the greater volatility of the former. The heat of formation of P2O 6 from
elements is about 370 kcal., and the heat of solution in water to form
its
FIG. 3.
Structure of
Oe and As 4 Oe.
orthophosphoric acid, H 3 PO 4 is about 35 kcal. The pentoxide appears to exist in a number of forms, one of
,
which sublimes at about 350. The
vapor density of the higher oxide corresponds to the formula P4Oio even at 1500. Frequent mention has been made of the oxide as an extremely efficient drying agent.
Electronic formulas for the
acids arc given below
:
more important phosphorus
H
:
H H
O
P
: :
H p
:
P "
: :
:O ::O
acid
Hypophosphoric
H
c\ \j
*
H O
:
P "
:
H
Metaphosphoric
acid
o \s
H p
:
P p P p
: : :
:O:
acid
:O:
Orthophosphoric
acid
Pyrophosphoric
The formulas
hypophosphorous acid and phosphorous acid have been written with two and one hydrogen atoms,
for
51]
GROUP- V.< NITROGEN, PHOSPHORUS, ETC
229
respectively, attached to the phosphorus. This is in agreement with the fact that the former acts only as a monobasic
and the latter generally as a dibasic acid, and also that these acids all have
acid
about the same strength as phosphoric acid see Table XV), whereas the general
rule that the higher the posi-
tive
oxidation
state,
the
stronger the acid, would predict that they would be very weak acids, since phosphoric
only moderately strong. In other words, it seems probable that the

acid
is,
itself,
FIG. 4. Structure of
hydrogen attached to phosphorus serves to attract electrons, and thus increase the formal charge on the central atom.
TABLE XV
DISSOCIATION CONSTANTS OF PHOSPHORUS ACIDS
51. Salts of
hypophosphorous
acid,
H(H PO
2
2 ),
are ob-
tained by the action of phosphorus on an alkaline solution The free acid may be prepared by treating the (Par*. 47). barium salt with sulfuric acid. The acid is a strong reducing agent and a poor oxidizing agent
:
+ H P0 = H PO + 2H+ + 2H O + P = H PO + H+ + e~,
H
2 3 2
2<T, 0.50 volt
0.51 volt
When
acids*
heated,
it
The sodium
decomposes into phosphine and phosphoric salt, NaH 2 PO 2 is used in medicine

,
230
REFERENCE
[Ch. XI
under the
belief that
body and only partially ionized in solution. 52. Phosphorous acid, H 2 (HPO 3 ) is formed by the action of the trioxide upon cold water, or by the hydrolysis of the trichloride: PC1 3 + 3H 2 O = H 3 PO 3 + 3HC1. The further
,
tissues.
As mentioned above, the
phosphorus can thus be supplied to the acid is monobasic
The 4 P2O6 addition of the chloride gives the pyro-acid, acid decomposes upon heating to give pure phosphine and phosphoric acid. The acid is oxidized to phosphoric acid:
.
H PO + H O = H PO + 2H+ +
3 3
2 3
2e~,
is
0.3 volt
but a
first moderately strong oxidizing agent 2H+ + 2e~, (- 0.4) is probably 2H 3 PO 3 = H 4 P 2 O 6 step volt. The meta-acid, HPC>2, forms when phosphorus burns in air but it reacts with water to give the ortho-form. 53. Hypophosphoric acid, H 4 P2O 6 may be formed, mixed with phosphorous acid, by the slow oxidation of phosphorus It is tetrabasic, and its in a limited supply of moist air. P 2 O 4 does not give salts are relatively unimportant. H 4 P 2 O 4 with water: P 2 O 4 H 2 O = H 3 PO 3 + H 3 PO 4 The prod54. The Phosphoric Acids and Phosphates. uct of the addition of phosphorus pentoxide to an excess of water is a solution of the orthophosphoric acid, H 3 PO 4 This acid, or its hydrate, 2H 3 PO 4 -H 2 O, may be crystallized from the solution by evaporating under reduced pressure. The pure acid melts at 42.3 and the hydrate at 29.4. The acid is tribasic, and thus forms three series of salts. The
required as the
ionization constants for the acid are, respectively,
KI =
7.5
10~ 1(T 6.2 X 10~ The values for the 3 molal concentration of H+ in molal solutions of the follow10~ 4 Na 2 HPO 4 10~8 S PO 4 0.1; NaH 2 PO 4 2 ing are: Na 3 PO 4 10~ 13 Phosphoric acid is but a very weak oxidizing agent (Par. 52). In this respect, it differs greatly from the other
3
K* =
=
,
12
5 acids of the group.
made by heating phosphate rock with sulfuric acid: CasCPO*^

Impure commercial acid
is
pulverized
+ 3H
SO4
54]
GROUP
3
V. NITROGEN,
PHOSPHORUS,
ETC.
231
= 2H PO4 + 3CaSO
sulfate
4.
The
is
greater portion of the calcium

is
formed in the reaction
by
filtration.
The
acid
also
similar to the preparation of
precipitated and separated manufactured by a method the free element by heating
phosphate rock with carbon and sand, but differing in that air is introduced to
oxidize the phosphorus vapor to the pentoxide, which
is
CH+
10
10
absorbed in water.
10
The most important
HPOf
salts
of orthophosphoric acid are
the calcium compounds. The occurrence of enormous deposits of the slightly soluble tricalcium phosphate has Soluble been mentioned.
^
t
10
10
phosphate constitutes an important constituent of

soils
fertile
and large quantities
j_
of
FIG
10
cc. of 0.1
20
30
40
phosphate rock (U. S. production about 7,000,000 tons yearly) are mined and converted into the soluble
M NaOH added
5.
Titration curves for phosphoric acid.
salt, Ca(H 2 P0 4 ) 2 for use as ferCa 3 (PO 4 ) 2 + 2H 2 SO 4 + 4H 2 = Ca(H 2 PO 4 ) 2 + 2Catilizer: SO?2H 2 O. The mixture of acid phosphate and gypsum is sold under the name of "superphosphate of lime." Triple superphosphate is made by the action of phosphoric acid on phosphate rock, Ca 3 (PO4 ) 2 + 4H 3 PO4 = 3Ca(H 2 PO 4 ) 2 It seems likely that ammonium phosphate will to a certain
, .
extent replace the superphosphate as a fertilizer (Par. 17). Most of the normal orthophosphates are but slightly
soluble.
The compounds, ammonium magnesium phos-
4 PO 4 -6H 2 O, and ammonium phosphomolybphate, date, (NH 4 ) 3 PO 4 -12MoO 3 are mentioned under analytical
MgNH
properties.
Microcosmic
salt,
Na(NH )HPO4
4
is
used in
232
REFERENCE
[Ch. XI
bead tests similar to the borax bead. The disodium phosphate, Na 2 HPO 4 -12H 2 O, is employed as a laboratory reagent. This compound loses water upon heating, forming, Sodium and calcium at about 95, the anhydrous salt. diacid phosphates are used in one type of baking powder. If the ortho-acid is heated to 215, water is lost and = H 4 P2O 7 + H 2 O. pyrophosphoric acid is formed: 2H 3 PO 4
When
dissolved in cold water, the rate of transformation back into the ortho-acid is slow, but the transformation is rapid in hot water. Hydrolysis does not occur
this acid
is
All four hydrogen ions are and the four ionization constants replaceable by metals, 2 7 are: Ki - 1.4 X KT K, = 1.1 X 1(T K, = 2.9 X KT
in neutral or alkaline solutions.
1
,
K* =
The silver salt, Ag 4 P 2 O 7 is but slightly 10~ and the magnesium salt, Mg 2 P 2 O 7 is of analytical soluble, importance. Sodium pyrophosphate is readily formed upon The heating disodium hydrogen phosphate, Na 2 HPO 4 be distinguished from the other phosphoric pyro-acid may acids through the formation of a precipitate with zinc
3.6
acetate.
Metaphosphoric acids, (HPO 3 )n are formed by strongly heating the ortho- and pyro-acid, and sodium salts may be
prepared by heating NaH 2 PO 4 Na 2 2 P 2 O 7 or NaHNH 4 PO 4 There is no good evidence for the existence of the monomer, HPO 3 but the di, tri, tetra, and hexapolymers of the acid or their salts have been prepared. Dimetaphosphoric acid may be prepared by heating H 3 PO 4 a short time at 300. It is soluble in water but hydrolyzes rapidly to the pyro,
phosphate.
The
is
lead
salt
is
slightly
soluble.
When
~
heated for several hours at 500, sodium It is readily trimetaphosphate, NasPsOg, is formed. soluble in water and gives no precipitate with Ag+ Pb~K or
2
NaH PO
from the copper salt by treatment with H 2 S. It is readily "" and Ca"4 4 but soluble and gives precipitation with Pb"
"
"
1
Ca4"*. Copper tetrametaphosphate is prepared by heating CuO and H 3 PO 4 up to 400. The free acid may be obtained
1
55]
GROUP
V. NITROGEN,
PHOSPHORUS,
ETC.
233
Sodium hexametaphosphate Na 6 P 6 Oi 8 is by fusing a sodium metaphosphate at 650 and prepared

not with
.
,
Ag+
then quenching.
(973 g./liter
2
The
at
salt
is
HO
salt
20). The
readily soluble in water lead salt is slightly soluble.
The sodium
has commercial importance in water
TABLE XVI
REACTIONS OF PHOSPHORIC ACIDS
softening and scale removal because
with calcium
it forms a complex This complex is so stable that solutions of the hexametaphosphate will decompose Portland cement by the removal of the calcium. Insoluble high polymers (molecular weight around 100,000), known as Kurrols salt, are formed by heating NaH 2 PO 4 below
ion,
Na Ca
2
P6Oi 8
fusion for long periods. The sodium salt of triphosphoric acid NasPsOio is formed Like the 4 2 PO 4 and Na 2 by heating mixtures of
NaH
HPO
forms complex ions with calcium. hexametaphosphate A series of fluophosphoric acids may be prepared by the substitution of oxide by fluoride, e.g., monofluophosphoric hydroacid, H 2 PO 3 F; difluophosphoric acid, HPO 2 F 2
it
;
fluophosphoric acid,
55.
HPF
6.
The Peroxyphosphoric
Acids.
H PO
3
,
and
HPO
4
(compare Peroxysulfuric Acid), are formed by the electrol4 2 containing a little ysis of solutions of the salt, fluoride and dichromate. The former is the prinpotassium
K HPO
cipal product at high current density and the latter at lower current densities. The former may also be" prepared by
234
REFERENCE
[Ch. XI
treating the pentoxide with cold 30 per cent hydrogen

peroxide.
Oxides and Acids of Arsenic. The trioxide, As 2 O 3 4 6 generally known as white arsenic, is commercially the most important compound of the element (cf. Fig. 3). Its most important source is the flue dust of smelters roasting arsenic-containing ores, and it is recovered from the dust by resubliming. The vapor condenses to a vitreous form which slowly changes to an octahedral crystalline modification. A monoclinic form may be prepared by heating for some time at 200. The oxide is slightly soluble in cold water and more soluble in hot water. The rate of soluThe solution contains tion in both cases is very slow. The acid is but slightly ionized, arsenious acid, H 3 AsO 3 KI = 6 X 10~ 10 About 60 per cent of the white arsenic consumed in the United States (40,000 tons per annum) is used in the manufacture of insecticides, 25 per cent in the manufacture of weed killers, and about 5 per cent in the manufacture of glass. Smaller quantities are used in the preparation of ant paste and rodent poison, as a mordant in dyeing, and as a wood preservative. The fatal dose of the oxide is 0.06-0.2 g., but a toleration may be developed that
56.
,
(As O ),
permit the consumption of several times this amount without harmful effects. A number of organic arsenic compounds are used in medicine, which are highly toxic to lower organisms, but which can be tolerated in fairly large quantities by the human body. Although the trioxide is somewhat amphoteric, it is more acidic than basic and dissolves readily in alkalies forming arsenites. Salts of the types Na 3AsO 3 NaAsO 2 and Na 2 As4O7 may be obtained, but the free poly-acids are not stable and decompose to give the oxide. The soluble salts are highly hydrolyzed, due to the weakness of the acid.
will
, ,
Ferric and magnesium arsenites are very slightly soluble, and suspensions of the hydroxides of these ions are administered in cases of arsenic poisoning. Sodium arsenite is used
58]
GROUP
V. NITROGEN,
PHOSPHORUS,
ETC.
235
extensively in the preparation of poison bait for grassnumber of hoppers, crickets, beetles and as a weed killer.
copper arsenites are important insecticides such as Paris green, Cu 4 (C 2 3O2)2(AsO3)2,
and pigments, and Scheele's
green,
CuHAsO
3.
trioxide dissolves in concentrated hydrochloric acid to form a trichloride, but this compound is completely hy-
The
drolyzed in dilute acid solution. Arsenious acid may be oxidized to arsenic acid
H AsO + 2H O = H AsO + 2H+ +

3 3 2
2<r,
0.559 volt
is evident from the potential value, a fairly strong oxidizing agent is required. In neutral solution the reaction with iodine is quantitative, but in acid solution, the reaction is reversed and arsenic acid oxidizes iodide quantitatively.
As
value of arsenite couple.

57.
0.234 volt is given in

is
Table XI
for the metal-
obtained upon evaporating a dissolving the trioxide in nitric acid. It as 2H 3 AsO 4 -H 2 O. When heated, water is lost crystallizes to form the pentoxide, As 2 O 6 which readily dissolves again in water to form the acid. Arsenates resemble the phosphates in solubility and crystalline form. The sodium salts, Na 2 HAsO 4 and Na4 As2C>7, are used in the preparation of the lead arsenates, Pb 3 (AsO 4 ) 2 and PbHAsO 4 and the corresponding calcium arsenates. The former are employed extensively to provide protection against fruit insects, and the latter for controlling the cotton boll weevil. The value of arsenic as an oxidizing agent has been discussed above. The so-called tri68. Oxides and Acids of Antimony. oxide, Sb 2 O 3 (or Sb 4 O6 ), together with some tetroxide, is formed when antimony burns in air. The tetroxide may be prepared from the trioxide by heating in air to moderate temperature (300^00), but at higher temperatures (about
solution
Orthoarsenic acid
made by
900)
it
decomposes again to the
trioxide.
The
trioxide is
236
REFERENCE
[Ch. XI
amphoteric.
It dissolves in
concentrated acids, but only
basic salts can ordinarily be crystallized from the solutions, In hot (SbO)NO 3 and K(SbO)C 4 4 O6 e.g. (SbO) 2 SO 4
, ,
water, these salts are completely hydrolyzed. The basic radical, SbO, is known as antimonyl, and the potassium antimonyl tartrate has long been used in medicine under the
name
of tartar emetic.
The antimonyl
"1"1
".
ion gives only a very
small concentration of Sb 4
The trioxide dissolves in alkalies, forming salts of antimonous acid. The sodium metaantimonite, NaSbO 2 -3H 2 O,
may be crystallized from the solution in sodium hydroxide. Salts of the ortho- and pyro-acids are also known.
The tetroxide is acidic in
but not acids.
2
properties, dissolving in alkalies,
Two CaSb O 5 and CuSb O

2
hypoantimonates occur as minerals,

6.
Antimony pentoxide,
arsenic,
like
may
.
be prepared by
the corresponding oxide of the action of nitric acid upon
the trioxide.
Antimonic acid appears to have the formula
acid are only slightly soluble in but they dissolve easily in alkali. The so-called potaswater, sium acid pyroantimonate, probably KSb(OH) 6 is very soluble in water, but the corresponding sodium compound is the least soluble of all sodium salts, and is sometimes employed as a test for sodium. As the solubility is about 0.03 g. per liter, the test is not delicate. The acid is a good
,
HSb(OH) 6
The oxide and
oxidizing agent:
SbO +
+ 5H O = HSb(OH) + 3H+ +
2
6
2er ca
;
0.7 volt
69. Bismuth Oxides, Hydroxides, and Acids. Bismuth monoxide is prepared by heating basic bismuth oxalate: (BiO) 2 C 2 O4 = 2BiO + 2CO 2 It is readily oxidized to the sesquioxide. The latter oxide occurs in nature, and may be formed upon heating the metal in air. It has a yellow color, a comparatively high melting point, and exists in several
.
crystalline modifications. but dissolves in acids, and
This oxide is not soluble in bases normal salts may be obtained by
61]
GROUP
V.
NHROGEN, PHOSPHORUS, ETC
237
evaporating the acid solutions. When treated with water in the absence of acid, these salts are hydrolyzed to basic compounds, e.g., basic nitrate (also called subnitrate), basic sulfate, (BiO) 2 SO4 and oxychloride, 3 Bi(OH) 2 A basic carbonate is known, and this and also the BiOCl.
NO
basic nitrate, are employed in medicine in the treatment of infections of the alimentary canal. The hydroxide,
is precipitated from the salt solutions by alkalies. not soluble in excess of the reagent. The hydrolysis of Bi"f++ gives some bismuthylion, BiO+, but complex ions such as Bi 2 O~H and Bi 3 O 2 f5 may also be present. Bismuthyl ion is readily reduced to the metal (cf.
BiOOH,
It is
"
Par. 66).
60.
Bismuth pentoxide, Bi 2 O 6
is
formed by the action of
very strong oxidizing agents upon the trioxide, e.g. NaCIO in weakly alkaline solution. It is comparatively non-reacIn concentrated sodium hydroxide it forms sodium tive. In water or acid, this compound bismuthate, NaBiO 3 hydrolyzes to the acid, which is a very powerful oxidizing
.
agent
BiO+
4-
2H O = HBiO + 3H+ +
2 3
2<r;ca
1.6 volts
The
manganous ion to permanganate Orthobismuthates are not known, although a tetroxide, BiaO 4 which is formed along with the pentoxide by the action of chlorine in alkaline solution upon the trioxide, is considered to be bismuth orthobismuthate, Bi(Bi0 4 ).
in acid solution.
,
acid will even oxidize
Halogen Compounds. The various halogen compounds are summarized on page 238. The halides may, in general, be prepared by the direct action of the elements. The compounds, AsX 3 SbX 3 and BiX 3 may also be prepared by treating the corresponding
61.
, ,
oxide with the concentrated halogen acid. The relatively unstable PC1 2 is formed by passing an electric spark through mixtures of PC1 3 vapor and hydrogen.
238
REFERENCE

TABLE XVII
[Ch. XI
HALIDES OF PHOSPHORUS, ARSENIC, ANTIMONY, AND BISMUTH X = any halogen
nature of the compounds increases with the elements of the group thus phosphorus is a non-conductor of electricity, while molten trichloride bismuth trichloride conducts readily. The halides are hysalt-like
The
increasing size of the
drolyzed by water, e.g., PC1 6 + 4H 2 O = H 3 PO 4 + 5HC1. Often an oxyhalide forms as the first step, e.g., POC1 3 SbOCl, and BiOCl. The more basic the oxide, the less is the tendency of the halide toward hydrolysis thus the hydroly,
:
sis of
antimony and bismuth
trichloride at ordinary
tem-
peratures stops at the oxychloride, and the reaction is readily reversed by acid. On account of its ready hydrolysis,
phosphorus trichloride is used extensively in organic chemistry to replace hydroxide by chloride, e.g. 3CH 3
COOH
PC1 3 =
3CH COC1 + H PO
3
3
Antimony
trichloride
early received the name of butter of antimony and was employed for medicinal purposes. It was prepared by the
reaction
:
Sb 2 S 3
3HgCl 2 = 3HgS
2SbCl 3
Bismuth
tri-
iodide
soluble in excess iodide, forming salts of the complex iodide BiI 4~. The antimony tetrachloride is known
is
only in complex
62. Sulfides.
salts.
The
following sulfides are
known
62]
GROUP
V.
NITROGEN, PHOSPHORUS,
ETC.
239
sulfides of phosphorus may be prepared by heating together the elements in equivalent amounts. Only two of
The
the
compounds, P 4 Si
is
,
and
P 4S 3
are
important.
The
used as a reagent in organic chemistry. The trisulfide, P4S 3 has been mentioned in connection with the manufacture of matches. P 4Si reacts with BiF 3 to
pentasulfide
form the sulfofluoride

It
PSF 3
Arsenic monosulfide, AsS, occurs as the mineral realgar. may be formed by heating together the elements, or by the reaction: FeS 2 + FeSAs = 2FeS + AsS. The yellow trisulfide, As 2 S 3 also occurs as a mineral, orpiment. It is
,
precipitated from solutions of arsenites by hydrogen sulfide. With pure arsenious acid, the precipitate is colloidal, but is
coagulated by hydrogen ion or other positive ions. The sulfide is not soluble in concentrated hydrochloric acid. The sulfide is acidic in nature and dissolves in excess sulfide In ion, forming thioarsenite : As 2 S 3 + 3S~~ = 2AsS 3 it is oxidized to thioarsenate : As 2 S 3 + 2S 2 polysulfide, The yellow trisulfide changes to a red + S = 2AsS4
.
form at 170. The pentasulfide, As 2 S 5 is formed by passing hydrogen sulfide into an acid solution of an arsenate. It is soluble in sulfide ion, forming the thioarsenate: As 2 S 6 and is reprecipitated from this com+ 3S = 2AsS4 acid. The sulfide is not very stable and decompound by poses rather easily into the trisulfide and sulfur. The mineral stibnite, Sb 2 S 3 is black, but the antimony trisulfide, precipitated from solutions of the trichloride or
,
orange red. It is soluble in concentrated hydrochloric acid, but not in dilute. It dissolves in sulfide and polysulfide, forming thioantimonites and thioantimonates, similar to arsenic trisulfide. When the thioantimoantimonites,
is
nates are acidified, the tetrasulfide and sulfur are precipitated: 2SbS 4 + 6H+ = Sb 2S4 + S + 3H 2 S. The tetrasulfide forms a mixture of thioantimonite and thioantimonate with excess sulfide ion, and is soluble in concentrated acid.
240
REFERENCE
[Ch. XI
Black bismuth sesquisulfide is formed by heating together the element or by the action of hydrogen sulfide upon bismuth salts. It is not soluble in dilute hydrogen ion, but is dissolved by hot dilute nitric acid with the oxidation
of the sulfur.
63.
(1)
It is
not soluble in sulfide or polysulfide.
Metal Compounds. Phosphides may be prepared by heating together phosphorus and the finely divided
or, (2)
metal
rus, or (4)
metal oxide; or by the action of (3) phosphophosphine upon solutions of metal salts. Exare
,
amples of
bronze),
3
,
(1)
2
K
2
Hg P
3
;
4,
MnP
2,
;
Sn 3 P (used
(3)
in
3
phosphor
(4)
P 6 PbP 6
(2)
Ca 3 P 2
Ag
P,
Cu P 2 and
Hg P4 Cu
,
P.
all
metals at red heat, e.g., Antimony forms a series of compounds with an apparent oxidation state 2, e.g., CuSb, NiSb, ZnSb, PtSb 2 and also compounds of the
Arsenic unites with almost

, ,
CoAs 2 FeAs 2 Fe4 As 3 NiAs, MnAs.

;
3 state, e.g.,
Ag
Sb,
Mg Sb
3
2,
Cd 3 Sb 2 Fe Sb 2 Bismuth also
,
forms a number of metal compounds, not so many as antimony.
e.g.,
Mg Bi,
3
although
ANALYTICAL
64. Phosphorus compounds are usually detected and determined as phosphate, since nitric acid readily oxidizes all of the lower states to this ion. In the absence of heavy metals whose phosphates are insoluble in ammonia, the phosphates may be precipitated as magnesium ammonium phosphate, MgNH 4 PO4 by a solution of magnesium chloIn ride, ammonium hydroxide, and ammonium chloride.
,
quantitative determinations, this is ignited and weighed as 2 P2O7. Ordinarily the phosphate is precipitated in dilute nitric acid as the ammonium phosphomolybdate 3 PO4
Mg
+ 12(NH MoO + 21HNO (NH PO -12MoO + 21NH NO + 12H O. This precipitate is usually not
4) 2 4
3) 2
weighed as such but is (1) dissolved in ammonium hydroxide and the phosphate reprecipitated as MgNH 4 PO4 or (2) titrated with standard hydroxide: (NH 4 ) 3 P04 -12MoO 3
64]
GROUP
V. NITROGEN,
PHOSPHORUS,
ETC.
241
I-
23OH- = HPO4
" + 3NH<+
much more The reducing
+ 12MoO
+
is
11H 2 O.
-A colorimetric determination of phosphate is based upon the fact that the 3 in the phosphomolybdate is reduced
MoO
to
molybdenum
blue
readily than
a solution
of molybdic acid. dine or stannous chloride.

slight solubility of
agent employed is benziAdvantage may be taken of the

,
bismuth phosphate, BiPO 4 to remove phosphate from acid solution. This is desirable in qualitative analysis since the presence of phosphate results in the precipitation of many slightly soluble compounds, e.g.,
CaHPO when NH OH
4,
4
is
added.
Arsenic, antimony, and bismuth are usually detected by precipitation as sulfides in dilute acid solution.
erties of these
The prop-
compounds have been discussed, and the systematic scheme of separation (Append. VI) should also be consulted for the outline of the analysis. Arsenic is sometimes determined quantitatively as the ammonium arsenomolybdate similar to phosphate given above. It is more often determined by the oxidation of arsenite to arsenate in
the presence of bicarbonate by iodine. Antimony may likewise be determined by the oxidation of antimonite to antimonate by iodine in alkaline solution, or better by the reduction of antimonic acid by iodide in acid solution. Bis-
muth may be
trioxide.
precipitated and weighed as the oxychloride, BiOCl, or precipitated as the hydroxide and weighed as the
Small quantities of arsenic and antimony are determined by the Marsh test, in which arsine and stibine are formed by reduction with zinc in hydrochloric acid, and the mixture of the gases with hydrogen passed into silver nitrate solution. Any antimony present is precipitated as silver antimonide, while the arsine is oxidized to arsenious acid. Upon filtering, the arsenic is confirmed in the filtrate by reprecipitation as sulfide, while the antimony in the precipitate
dissolved in hot concentrated tartaric acid and then reprpcipitated as the sulfide. The test for arsenic may be modiis
242
REFERENCE
[Ch. XII
separating the arsenic from the antimony by volatilizing the former as AsCl 3 from a hydrochloric acid solution, and then, after reduction with zinc, detecting the
fied
by
first
by placing a strip of paper wet with copper sulfate solution in the stream of gas. From the depth of color of
arsine
the copper arsenide formed on the paper, the quantity of arsenic may be estimated. The method is capable of detecting 0.001 milligram of arsenic. 65. Potential diagrams. For comparison of the group
properties the following potential diagrams are given for acid solution:
-3
-
+3
0.27
+4
1.07
+5
0.81
1.44
NH
N
0.06
HNO
|
NO - 0.94
2
NO 3
|
0.49
P
0.54
H PO
3
|
(3
0.40)
H PO
2
(0.9)
3
H PO
3
|
0.30
As
0.247
0.56
H
0.212
0.51
0.68
Sb 2O4
0.58
0.5
(0.8)
Bi
0.32
(-
1.6)
BiH 3
((1.6)
1.6)
Chapter XII
GROUP
1.
VI.
SULFUR, SELENIUM, TELLURIUM
AND POLONIUM
The
relation of the three elements, sulfur, selenium,
in
and tellurium to oxygen has been discussed
Chapter
is
II.
The outstanding
characteristics of these elements
the
and the tendency to add two more electrons to complete the octet. Thus the members of the group all form compounds with the electropositive elements, in which they exhibit an oxidation state of minus two, and with the more electronegative elements compounds in which the oxidation state varies from one to six, the most important of these being the + 4 and the + 6 states. The elements are all solids with relatively low melting points. Sulfur is distinctly a non-metal, but selenium and tellurium, A especially the latter, show certain metallic properties. marked characteristic of the group i,s the existence of a
six valence electrons
'
number
of allotropic modifications.
In addition to these
three elements, the extremely rare, unstable, and highly radioactive element, polonium, belongs to this group. The few known facts relating to its chemical behavior are given
in Par. 35.
Occurrence. The amount of sulfur in the earth's Most of this occurs crust is estimated at 0.1 per cent. rise to primarily as iron sulfide, but oxidation has given large deposits of sulfate, chiefly of calcium and magnesium.
2.
The
heavy metals, except gold and platinum, occur as minerals, the most extensive deposits being those of iron pyrites, FeS 2 Free sulfur occurs in numerous
sulfides of all the
.
943
244
REFERENCE

TABLE
I
[Ch. XII
deposits, of special importance being those in Louisiana Texas, and in Sicily.
and
Selenium and tellurium are much less abundant than sulfur, the estimated percentage in the igneous rocks being 10~8 and 10~9 respectively. The former occurs in the free
state in
most of the sulfur deposits, as selenides of many of the heavy metals, especially copper, silver, and lead; and less frequently selenites of copper, lead, cobalt, and other metals. Tellurium occurs chiefly as tellurides of copper, Tellurites and free lead, silver, gold, iron, or bismuth. tellurium are of rare occurrence.
THE FREE ELEMENTS

3.
Sulfur.
Sulfur vapor at the boiling point has a moleclargely S 2 and
ular weight of 230 and
At 1000
plexes
is
it is
into atomic sulfur.
common
mostly S8 with some S6 and S 2 is about half dissociated This tendency of sulfur to form comcharacteristic of the group and may be
is
,
at 2000
attributed to the readiness with which a sulfur atom, S:,
3]
GROUP
VI.
SULFUR, SELENIUM, ETC.
245
will share its electrons with other sulfur atoms in an effort to complete the octet. Liquid sulfur contains two molecular species called Sx and SM (probably S8 and ), and The possibly one or two others. structure of S8 is an eight membered
ring with the
S-S-S angle of
105.
FIG.
quent in liquids but the unusual feature with sulfur is the slowness with which the equilibrium state is reached. The time required is still further increased
1. Molecule of rhombic sulfur, S8

.
the equilibrium liquid conSM and at the boil35 per cent. The heat of ing point the transition is 416 calories. Such an equilibrium is probably not infretains 3.6 per cent
The S6 At 120
is
probably irregular chains.
by the presence of traces of iodine or sulfuric acid, but is decreased by ammonia. Near the melting point sulfur is a light yellow mobile liquid; as the temperature is increased it becomes darker and more viscous with increasing content of SM The viscosity reaches a maximum around
.
rapidly as the boiling point is ap-
200, and
falls off
proached.
Solid sulfur exists in
crystalline forms,
two
2.
rhombic
and monoclinic, Fig.
There have been prepared, also, two other monoclinic, one triclinic and one rhombohedral form, but they are
FIG.
2.
Crystal forms of sulfur; sul(left) and sulfur monoclinic
common forms. There

colloidal
unstable with respect to the are also a
number of amorphous and
forms whose characteristics doubtless depend
chiefly
of dispersion. equilibrium with monoclinic at 96 C.
slow,
Rhombic sulfur is in The reaction is rather however, and by rapidly cooling sulfur, held for some
upon the degree
246
REFERENCE
[Ch.
XI
time just above its melting point, the long needle-shaped monoclinic crystals may be obtained. At room temperature they are transformed into rhombic in about a day. The heat of the transition is 70 cal. Rhombic sulfur melts at 112.8, in equilibrium with Sx and at 110.4 to form the
,
equilibrium mixture SXM Monoclinic sulfur melts at 119.2 Both forms are soluble in to form Sx and 114.5 to form Sx/i 25 the solubility of the monoclinic is 1.28 times that CS 2 At of the rhombic. The molecular form of the solute in both cases is S8 By heating sulfur near its boiling point, and suddenly cooling, a very plasTriple Point R-M-L, 161, 1288 atm. tic substance is obtained which consists of a mixture
.
and an form not soluble amorphous in carbon disulfide. The latter form is essentially the
of rhombic crystals
Rhombic
super-cooled
liquid.
After
becomes very hard. The rate of change of the amorphous into the rhombic form requires years at ordinary temperature, but Temperature is rapid at 90. There is at FlG. 3. Pressure-temperature dialeast one Other amorphous gram for sulfur; diagrammatic as actual vapor pressures are not known. modification, this form being soluble in carbon bisulfide. Finely divided sulfur prepared by precipitating sulfur from calcium polysulfide by the addition of acid is known as milk of sulfur, and finely divided sulfur formed by sublimation is known as flowers of sulfur. The various forms of sulfur are all non-conductors of electricity and are insoluble in water. 4. The salt domes of Louisiana and Texas have now sup* planted the mines of Sicily as the world's most important source of sulfur. These enormous domes consist of a salt core covered with a cap of gypsum, dolomite, and limestone
it
.
some time
*\
5]
GROUP
VI.
247
which the sulfur occurs. It is extracted by the ingenious Frasch Process. Water heated to about 180 under pressure is pumped down bore holes and forced into the deposits; the sulfur is liquefied, and when a quantity of it collects at the bottom of the cavity it is forced to the surface by an
in
air
is
lift and discharged into bins. A small amount of sulfur obtained from the purification of illuminating gas (Par. 8). The production of sulfur in the United States in 1948
was 4,000,000
sulfuric acid.
tons.
The major
portion of this
is
made
into
Smaller amounts are consumed in the vulcanization of rubber, in the manufacture of sulfites and
thiosulfates, in bleaching dried fruit,
and
for dusting
and
spraying plants. Sulfur is both a fairly good reducing agent and oxidizing agent. It combines directly with all of the elements except gold, platinum, and the inert gases. 5. Selenium. Selenium vapor at the boiling point conThe liquid also doubtless Se 2 sists of mixtures of Se 8 contains a number of molecular complexes but the problem has not been carefully investigated. The solid exists in
.
three crystalline modifications, two of them rather similar monoclinic forms, red in color, soluble in carbon disulfide, and unstable with respect to the third form, a hexagonal
rhombohedral structure known as metallic or grey selenium. are relatively stable below 100 and melt somewhat below 200, the exact temperature being in doubt due to their rapid transformation, upon heating, into the grey form. The latter form melts at 220 and is insoluble in carbon bisulfide. Like sulfur, there is an amorphous vitreous and black in color, which may be modification, prepared by quickly cooling the liquid. Reduction of selenates results in the formation of two red modifications, one crystalline and the other amorphous. A number of colloidal forms of selenium have been prepared. The electrical conductivity of the grey form is poor, but is greatly increased by light. This property makes selenium
The monoclinic forms
248
REFERENCE
(Ch. XII
useful in the construction of apparatus for the measurement of light intensity, as in photometers for measuring the intensity of radiation coming from the stars, and for the
automatic turning of lights on and

respectively.
off at
night and morning,
Large quantities of selenium could be recovered from the burners in sulfuric acid plants, and from the anode mud of electrolytic copper refineries. The free element has no extensive commercial applications. The largest consumption is in the glass works for making ruby
flues of the sulfur
red glass, and to neutralize the green color of glass, due to the presence of ferrous silicate. Some selenium is used in place of sulfur in the vulcanizing of certain types of
rubber goods, and a small amount of selenium is added to copper alloys and stainless steel to make them more machinable.
The
reactions of selenium are similar to those of sulfur,

is
but the element
both a poorer reducing agent and a poorer oxidizing agent than sulfur, cf. Table II and Par. 13. 6. Tellurium. The vapor of tellurium at the boiling point contains a much smaller per cent of the higher molecular complexes than in the case of sulfur and selenium, being mostly Te 2 The solid crystallizes in a silver white, semi-metallic, rhombohedral form, isomorphic with grey selenium, and in a second modification as yet little known. It may be precipitated in an amorphous modification by
.
reduction and like the other members of the group readily forms various colloidal solutions. The amorphous form changes to the crystalline extremely slowly at ordinary
temperatures, but rapidly just below the melting point. The metallic modification is insoluble in carbon bisulfide. Its density is 6.24. It is the poorest electrical conductor of any of the metals, specific resistivity being 2 X 10" 1 ohm-cm.
Tellurium with an atomic number of 52 has a higher atomic weight than iodine, atomic number 53. This situation arises through a preponderance of the heavier isotopes of tellu-
8]
GROUP
VI.
249
num. Fairly large quantities of tellurium could be recovered from a number of metallurgical processes, especially the electrolytic copper refineries. Like selenium it imparts 0.05 per cent alloy with free-cutting properties to steel.
lead increases the corrosion resistance of that metal.

7.
Hydrogen Compounds.
The compounds,
2 S,
2 Se,
polar liquids than water, as is indicated by their lower melting and boiling points. Their stability decreases and their power as reducing agents (Table II) increases with increasing atomic weight; that is, with in2 Te, are
much
less
creasing size of the atom, it becomes easier to pull off the two extra electrons. Hydrogen selenidc and hydrogen
telluride are endothermic.
These compounds
all
possess
very disagreeable odors and are extremely toxic.
TABLE
II
HYDROGEN COMPOUNDS OF SULFUR GROUP
8. Hydrogen Sulfide. Hydrogen sulfide may be formed by passing hydrogen into boiling sulfur, but is usually prepared by the action of acid upon a sulfide, particularly The gas is ferrous sulfide: FeS + 2H+ = Fe++ + H 2 S. extent of 290 soluble in water at 20 and 1 atm. to the volumes per 100 volumes of water. The resulting concen-
tration
is
about
0AM.
In solution,
first
7
,
it
behaves as an ex-
tremely weak
dibasic acid; the
= H+ = HS~, is 1.15 X 10~ 1.0 tion constant, HS~ = H+ + S
ionization constant, and the second ioniza-
10~ 16
The
soluble
250
REFERENCE
[Ch. XII
sulfides are, accordingly, highly hydrolyzed, taining about Q.Q85N OH~. The acid sulfides or
sulfides,
OAN Na
S con-
hydro-
such as NaSH, are
much
less alkaline; 0.17V
NaSH
contains 0.0017V
OH~.
presence of 10~W 10~ 16 lf, and at Q.3M H+ the sulfide concentration is 10-2 The concentration of sulfide in IM (NH 4 ) 2 S is 10~ 6 Af.
4"
saturated solution of 2 S in the has a sulfide ion concentration of
W.
The
main
sulfides of nearly all the metals except those of the groups I, II, and III are insoluble in water. Extensive
use is made in qualitative analysis of the varying degrees of solubility of the sulfides. Due to the weakness of hydrogen sulfide, the solubility of all sulfides is increased in acid.
However, certain of the
sulfides are so
extremely insoluble
that even large concentrations of hydrogen ion do not increase the solubility sufficiently to dissolve them in appreIn general practice the metal sulfides are + divided into two groups: (1) those precipitated in 0.3 by 2 S, and (2) those not precipitated under these condiciable amounts.
NH
tions.
For
details of the classification
and separation,
refer-
may be made to the general scheme of analysis, Appendix VI. Hydrogen sulfide burns in excess of air to form sulfur dioxide and water. In a limited amount of air, the free element is formed, as the dioxide and hydrogen sulfide react according to the equation :2H 2 S + SO 2 = 3S + 2H 2 O. Advantage is taken of the oxidation in a limited quantity of air to remove hydrogen sulfide from illuminating gas, where it is objectionable because of its odor and the corrosive nature of its combustion products, the process being carried out by admitting a small amount of oxygen and heating
ence
the mixture. The sulfur precipitated by the reaction as a by-product.
is
sold
Hydrogen
tion of
sulfide tarnishes the surface of
even such a
noble metal as silver:
2Ag
+H
is,
2S
= Ag 2 S +
2.
The
ac-
hydrogen
sulfide here as
the liberation of hydrogen
an oxidizing agent with of course, due to the great
$12]
GROUP
VI.
SULFUR, SELENIUM, ETC
251
stability of silver sulfide. The absorption of sulfur by the alkaline sulfides is discussed later under the polysulfides
(par. 26).
9.
Hydrogen Selenide and
Telluride.
The
direct
com-
bination of hydrogen with selenium and tellurium shows less tendency to take place than with sulfur: however, the reactions do proceed to some extent at high temperatures.
The compounds can be

tion of acid
upon
prepared, respectively, by the aciron selenide or upon magnesium or
are gases with very disagreeable water to form dibasic acids, probably slightly stronger than hydrogen sulfide. The selenides and tellurides of the heavy non-alkali metals are insoluble in water. Hydrogen telluride decomposes above 0. 10. Oxides. Sulfur forms the oxides SO, S 2 O 3 SO 2 SO 3 and SO 4 selenium SeO2 and SeOs (unstable) and tellurium
telluride.
aluminum
They
odors, and dissolve
in
TeO, TeO 2 and TeO 3 The slight tendency of selenium to form oxides is interesting in connection with the same
,
characteristic of bromine, which occupies a position but one atomic number higher than selenium (cf. X 12). The heat of formation of selenium ^dioxide is also less than
either of the others, the values in kcals. being:

71,
SO
(gas)
SeO 2 (solid)
56,
2
and TeO 2 (solid)

3.
77.6.
11.
SO and S O
Sulfur
reacts
sulfuric acid or with the trioxide to
with concentrated form the unstable solid
It is not an acid anhydride, although its sesquioxide, S 2 3 oxidation state corresponds to the hyposulfurous acid, 2 S 2 O4. When a mixture of SO 2 and sulfur vapor is subjected to an electrical discharge SO gas is formed. It is highly un.
stable.
is
H 2 O = H 2 S 2 O 4 + S. with water. 3SO Dioxide and Sulfurous Acid. Sulfur dioxide 12. Sulfur 10, It is formed by the a gas condensing to a liquid at
It reacts
oxidation of sulfur or sulfides, and

furic acid:
2H 2 SO 4
+ = S0 ;4FeS + 11O = 2Fe O + 8SO Cu = CuSO + SO + 2H 2 O. Due to the in2 2

2
by the reduction
2 2
3
of sul2
;
stability of sulfurous acid, the gas
is
liberated
by the action
252
REFERENCE

sulfites:
ICh. XII
of strong acids
upon
Na 2SO 8 + H 2SO4 = Na 2SO4
SO2 H2O. The gas is, however, moderately soluble in water, 50 volumes per unit volume of water at 20 and 1 atmosphere, forming sulfurous acid in solution. In terms of the electron structures, this reaction is:
:
6 +
:
H O H
:
:
==
H 6
:
6 H
:
:O
Sulfurous acid is a rather weak dibasic acid, somewhat resembling carbonic acid. Its first ionization constant is 0.012 and the second 6.2 10~~8 Sulfurous acid is a fair
oxidizing agent (Table III). It is unstable with respect to the decomposition: 3H 2 SO 3 = 2SO4 4H+ S 2 O;
~+
+H
slow but takes place under the influence of violet light and upon heating. Its most important reaction, however, is its oxidation to sulfuric acid (Table III). Many of its industrial uses depend upon this action as a reducing agent.
is
0.33 volt.
This reaction
TABLE
III
OXIDATION-REDUCTION POTENTIALS OF SULFUROUS AND SULFURIC ACIDS
+ 3H
-f
H aO - SO 4
H aSO + 4H+ + 4<r .............................

but
VOLTS
+ 4H+ + 2e~ ..........................
256
0.45 0.20
slightly hydrolyzed. The sulmetals are insoluble. The acid many heavy sulfites occur in two types, such as NaHSO 3 and Na 2 S 2 O 6 the latter being the anhydride of the former: 2HSO 8"" - S 2O 6 2 O. At 20, sulfur dioxide may be liquefied by a pressure of about 3 atmospheres. Because of its ease of liquefaction
alkali sulfites are
fites of
The
of the
+H
it is
in refrigeration processes. The commercial usually sold as the liquid, in metal cylinders. Sulfurous acid has a powerful toxic action upon vegetable
employed
is
product
organisms, and thus finds
many
applications as a fungicide
14]
GROUP
VI.
253
in the preparation of beverages and Sulfurous acid and sulfites are used extensively as bleaching agents for silk and woolen textiles, straw hats, feathers, and dried fruits. Sulfites have a digesting action upon wood, tending to separate the fibers as well as bleaching them, and their largest use is probably in the pulp and
and as a preservative
foods.
paper industry. 13. Selenium Dioxide and Selenites.
general of preparing sulfur dioxide are applicable to selenium dioxide. This dioxide is a solid which sublimes with-
The same
methods
out melting.
It
has a characteristic odor which

"
acid,
is
described
as that of "rotten horse-radish.
It dissolves in
water to
the
form weak selenious
SeO3.
Upon evaporating
solution, the free acid separates, and upon further heating, decomposes to the oxide. The acid is a much more powerful
oxidizing agent than sulfurous acid:
3H O +
2
Se
H SeO + 4H+ + 4er, 2

3
0.74 volt
thus oxidizes sulfurous acid to sulfuric: 2H 2 SOa + 2 SeOa Se + O. The selenium first sep+ 2 arates as a red transparent colloid. When a solution of selenious acid is boiled with hydrogen bromide, the volatile tetrabromide escapes. Some attempts have been made to use the selenites as insecticides in fruit orchards, but they are so extremely toxic that they damage the growing plants.
It
= 4H+ + 2SO 4
The
acid constants are: Ki, 2.4
X KT
and
K*
10~ 9
14.
Tellurium Dioxide and Tellurites.
Tellurium burns
readily than does selenium to form the dioxide. The dioxide is also formed by the action of other strong oxidizing
more
H+ = TeO 2 H+, soluble in acid, TeO 2 8.9 X 10~ . The acid may also be obtained by the oxidation of tellurium by nitric acid. Salts of the "tdluiyl"
oxide
is
agents upon the metal, and by reduction of tellurates. It does not unite readily with water but may be dissolved in alkali to form tellurites from which the slightly soluble acid may be obtained, upon acidifying, as a white solid. The
somewhat
3
254
REFERENCE

l
[Ch. XII
even Te4 O7" f are known. With hydro* gen iodide the acid forms the slightly soluble iodide, TeI4 The acid forms a number of acid complexes of the general
radical, TeO"^", or
.
"
formula,
H TeO3nTeO
2
dizing agent but
= TeO
+ 4H+ +
(or acid) is a fair oxinot so strong as selenous acid. 2H 2 Te 0.53 volt. It is not easily oxi40-,
2.
The oxide
O +
dized to telluric acid. The dioxide forms, upon heating with tellurium, the monoxide, TeO. This oxide may also be formed by the hydrolysis of the chloride, TeCl 2
.
Sulfur trioxide, is a colorless liquid, freezing at 15 and boiling at 46. SOg, The solid soon changes from a transparent glassy form to
16. Sulfur
Trioxide and Sulfuric Acid.
the polymer, S 2 O6, an opaque mass of needle shaped crystals which can be sublimed without melting. The trioxide possesses a remarkable affinity for water, forming sulfuric acid:
:
O
S
H
:
O
S
O "
+ O H=H O
:
:
O H "
:
This reaction takes place with a hissing sound resulting from the large quantity of heat evolved, 38 kcal. The trioxide dissolves in concentrated sulfuric acid, forming the bi- or pyrosulfuric acid, H 2 S 2 O7, called "fuming sulfuric acid" or "oleum." 16. Contact Process. Sulfur trioxide is formed by the
action of oxygen (air) or other powerful oxidizing agents ?O 2 = SO3 has, upon sulfur dioxide. The reaction, SO 2
at 25
volt.
partial pressures of 1 atm., a potential of 0.35 Like many direct oxidations by O 2 this reaction is
,
and
extremely slow.
However, the rate can be increased by
certain surface catalysts, including ferric oxide, vanadium pentoxide, and metallic platinum, the latter two being very This catalysis is the basis for the "contact effective.
process" for the manufacture of sulfuric acid. The efficiency of platinum as a catalyst increases with temperature,
16]
GROUP
VI.
SULFUK, SELENIUM, ETC.
255
reaching a maximum about 500, but the per cent of trioxide formed at equilibrium decreases at high temperature
(Table IV).
TABLE IV
EQUILIBRIUM CONSTANTS FOR THE REACTION, SO 2
+ JO
* SO 3
generally carried out between 380 and 450 air, under which conditions 97 to 99 per cent of the dioxide is converted into trioxide. The efficiency of
reaction
is
The
with excess
The platinum
the catalyst depends upon the extent of active surface. is obtained in a finely divided state by heating chlorplatinic acid, H 2 PtCl 6 and is dispersed upon a base of asbestos fibers, magnesium sulfate, or silica gel. In recent years the cheaper vanadium pentoxide has replaced
,
of the platinum. One of the factors in the successful operation of the process is the removal from the sulfur dioxide of all impurities
much
which
"poison" the catalyst and render it inactive. important to remove traces of solid sulfur, selenium dioxide, mercury, and compounds of phosphorus
may
It is particularly
and arsenic. The sulfur trioxide formed by the reaction is more readily absorbed from the excess of oxygen by concentrated sulfuric acid than by water. The discovery of
this curious fact aided materially in the
development of
the process. The explanation appears to be in the formation of a fog through the absorption of water vapor by the sulfur trioxide when water is used as the absorbing medium.
fog particles are small drops of sulfuric acid, and their thermal motion, compared with gas molecules, is very slow. With concentrated sulfuric acid, no fog is formed, and the
The
moving sulfur trioxide molecules are more readily absorbed when the gas is bubbled through the acid. As the trioxide dissolves, water is added to keep the acid at
rapidly
256
REFERENCE
[Ch. XII
desired concentration, usually at about 98 per cent One of the mechanical problems is the temperature control. Since the reaction liberates heat, the temperature
any
acid.
kept from becoming too high by means of heat interchange between the incoming and outgoing gases. The reaction is carried out in cast iron containers, iron being insoluble (passive) in concentrated sulfuric acid.
is
17.
Lead Chamber Process.
Many
industries
employ
dilute sulfuric acid of no high degree of purity. It is cheaper to make this type of acid by the action of oxygen and steam
sulfur dioxide, using nitric oxide as a catalyst. This process is known as the lead chamber process, from the large lead-lined reaction chambers employed. The presence
upon
of steam increases the ease of oxidation of sulfur dioxide, = 2S04 1.1 volts at 25 C., as comSO 2 2 2O
+H
pared to 0.35 volt for the oxides. Although the various steps involved in the action of the gases with the catalyst are apparently quite complicated, the net result is that the nitric oxide acts as an oxygen carrier
:
NO + i0 = N0 NO + SO + H O = NO + H S0
2
The
reaction
is
carried out in
immense
lead chambers of
approximately 200,000 cu. ft. capacity. The sulfuric acid condenses and is drained off at the bottom of the chamber. The nitrogen oxides are recovered by passing the gas coming from the lead chamber through concentrated sulfuric
acid.
The probable
reaction
is:
is
N O + 2H SO = ONH2 3
SO 4
+H
O.
This reaction
reversed
acid,
upon
dilution;
4
,
the water and nitrosyl
sulfonic
ONHSO
again
forming sulfuric acid and nitrogen oxides. Advantage is taken of this reversal to restore the oxides of nitrogen to
the system by diluting the nitrogen containing acid, and by passing the sulfur dioxide, which also aids in the reversal 2 by removing through the solution before entering the lead chambers. This is carried out in a large tower employ-
NO
18]
GROUP
VI.
257
ing the counter current principle. Thus the nitrogen oxides are again restored to the chambers and at the same time the chamber acid is concentrated. The ordinary chamber acid is about 60 to 70 per cent sulfuric acid and large quantities
are sold at these concentrations.
tion
may
Further concentrabe carried out by evaporating in lead pans until
a concentration of 77 per cent is reached. Below this concentration the lead is not rapidly oxidized because of a
protective layer of sulfate. Above this concentration, however, the sulfate is soluble, and the concentration process
is
usually continued in iron vessels.
The
use of
silica
and
silicon iron containers for the further concentration is be-
coming more general. Formerly a large fraction of the sulfur dioxide consumed in the manufacture of sulfuric acid in this country was made by roasting iron pyrites, FeS 2 but at present the major portion is made by burning sulfur. However, two thirds of the world's production of sulfuric acid is still made from pyrites. Some sulfur dioxide is utilized from the stacks of the copper, zinc, and lead smelters.
,
18. Properties of Sulfuric Acid. The specific gravity of sulfuric acid solutions increases rapidly with concentration, becoming 1.85 for 100 per cent acid. The pure acid melts
at 10.5, but the melting point is greatly lowered by the presence of either water or sulfur trioxide. The boiling point is 270 at 755 mm., but is without special significance
since the solution loses sulfur trioxide
and changes
in
com-
position until the constant boiling mixture of 98.3 per cent In addition to the comsulfuric acid is reached at 338.
pounds,
freezing
SO 3 -H 2 O, (H 2 SO
4)
and 2SO 3 -H 2 O, (H 2 S 2 O 7 ), the
SO -2H
3
point curves, Fig. 4, indicate the hydrates, O, SO 3 -3H 2 O, and SO 3 -5H 2 O. The great stability of these hydrates renders sulfuric acid an excellent dehy2
drating agent.
The concentrated
(C 6 Hi
from
cellulose,
22
carbon: Ci 2
H On
6)n ,
acid will remove water and sugar, Ci 2 H 22 On, depositing

It,
= 12C + 11H 2 O.
however,
is
not as
258
REFERENCE
[Ch. XII
powerful a dehydrating agent as phosphorus pentoxide, since this oxide will liberate sulfur trioxide from sulfuric H 2 SO 4 = 2HPO 3 SO 3 The heat of soluacid: P 2 O 5 tion of sulfuric acid in a
large
amount
second
of
water is 19.0
is
kcal. Sulfuric acid
dibasic
the
S2 8
ionization
is
somewhat weak, the constant being 0.012 at 25 C. In 10M 2 SO 4 the percent-
so.
age of
SCU
are
2,
HSOr", and
H SO
2
68 and 30 while
20
40
60
80
100
Per centS0 3
FlG.
4.
trioxide
The sysstem sulfur and water.
pure sulfuric acid is 98 per cent H 2 SO 4 and 2 per cent HSO 4~. At molal concentrations the potential of the acid as an oxidizing agent is not very great (Table III), but the energy of concentration is so large that the oxidizing power of the concensufficient
trated
acid
becomes very strong,
to dissolve
copper or silver.
TABLE V
CONSUMPTION OF SULFURIC ACID IN U.
(Tons of
Fertilizers
S. IN
1946
100%
Acid)
3,020,000 755,000 1,000,000 1,780,000 510,000 550,000 556,000 105,000 75,000
Metallurgical
Petroleum Chemicals Coal products Paints and pigments

.
Rayon and cellulose

Explosives
Textiles
The distribution of the more important consuming industries is 2 SO4 among given in Table V. Sulfuric acid has played a leading role
19. Applications of Sulfuric Acid.
"20]
GROUP
VI.
259
in the industrial development of the past century, due to its low cost of production and various useful chemical
properties.
The high
boiling point accounts for its use in
displacing
fluoric,
it is
more volatile acids such as hydrochloric, hydroand nitric acids from their salts. As a strong acid,
used to convert calcium phosphate to acid phosphate
for fertilizer, to dissolve base metals and oxides, to clean metal surfaces prior to galvanizing and tinning, and to neutralize ammonia in its recovery from coke ovens and
an
the packing industries. As a dehydrating agent, it plays essential role in the manufacture of explosives, celluloid,
pyroxaline, varnishes, ether, etc. The nitration process liberates water which is removed by the sulfuric acid thus allowing the reaction to go to completion. Many of its applications depend upon the oxidizing power of the concentrated acid, e.g. in removing tars and organic sulfides from
petroleum.
The
insolubility of
many
sulfates
is
another
factor of industrial importance, as in the manufacture of the important pigment, lithophone, a mixture of barium
sulfate
and zinc
sulfide.
,
Pyrosulfuric acid, H 2 S 2 O 7 is used when the acid in its most powerful oxidizing and dehydrating form is desired. It was employed during the Great War to form "smoke screens/* since it forms a very stable mist or fog composed
of tiny drops of sulfuric acid. 20. Sulfates. As a dibasic acid, sulfuric acid forms both
neutral and acid salts. The acid salts to form the pyrosulfates 2NaHSO4
:
may be dehydrated = Na S O + H 0.
2
2
The normal
salts of the alkali
and alkaline earth metals
and lead do not
readily
decompose upon heating, but the

if
sulfates of the nobler metals evolve sulfur trioxide, or sul-
fur dioxide and oxygen

is
the decomposition temperature

of ferric sulfate
was once an important method of preparing sulfur trioxide and sulfuric acid. Sulfates are reduced by heating with carbon to form the sulfide: Na 2 SO 4 + 2C = Na 2 S + 2CO 2 Barium and
high.
The decomposition
260
REFERENCE
[Ch. XII
lead sulfates are
sulfates (Par. 32).

solubility
is
~ slight weakness of the HSO 4 ion. Many of the solid sulfates crystallize with an odd number of water molecules, In this example four water molecules e.g., CuSO 4 -5H 2 O. are attached to the copper and the fifth is attached to the
among the more important insoluble Though insoluble in dilute acids, their increased in concentrated sulfuric acid by the
O
sulfate
by hydrogen bonds,
\/ S
O H
\
O.
O
21. Selenic Acid.
O H
Rather powerful oxidizing agents, such
as
PbO2 or C1 2
are required to oxidize selenous to selenic
acid,
2
even in dilute solution:

2
HO +H
SeO 3 = SeO4
+ 4H+ +
2<r,
1.15 volts
concentrated, is a very powerful oxidizing agent, liberating chlorine from chloride, and dissolving gold, but not platinum unless chloride is present.
Conversely, selenic acid,
when
The
however, slow with many reducing agents, e.g. H 2 S and SO 2 but is faster in the presence of chloride. The free acid is easily prepared by the action of bromine
reaction
is,
,
upon
silver
selenite:
Ag 2 SeO3 + H O + Br =
2
2AgBr. The pure
acid melts at 58
and
its
2 HjjSeO* concentrated
When dehydrated, it gives is thick and sirupy. selenous oxide and oxygen. The solubilities of the selenates The soluble selenates are, are similar to the sulfates.
solution
however, easily distinguished from sulfates by their higher In a high voltage discharge, selenium oxidizing power. reacts with O 2 to form the very unstable SeOs. 22. Tellurium Trioxide and Telluric Acid. Telluric acid
forms
acidic.
salts of the
is
types
Ag6TeO 6 and Ag TeO 4

2
The
2
acid,
HeTeOe,
but
Upon
sparingly soluble in water, and is heating, it loses water to form
H TeO
but weakly
4
and
24]
GROUP
VI.
261
then TeOa. The trioxide does not react with water. acid is a good oxidizing agent,
The
4H O + TeO 2 (s) = H TeO6 (s) + 2H+ +

2
6
2<r,
1.02 volts
The
ability of tellurium to hold
more than the customary
is interesting four oxygen atoms, as is shown in 6 TeO 6 in connection with the same property of iodine and an,
timony, which occupy the neighboring position in the

periodic table.
23.
Other Sulfur Acids.
very large number of com-
plex acids of sulfur exist,

:
H 6
:
p
S
O
S
O
S
O H
:
H O "
:
O "
"
:S
Hyposulfurous acia
:S:"
Hydrogen
polysulfide
Thiosulfuric acid
H:O:S :S:O:H H :O
Dithionic acid
:S :S :S:O:H
H :O:
S :S :S S :O :H
:
Trithionic acid
Tetrathionic acid
6
S
H O
:
O O
:
O H
:
H O
:
:O
:O
:O
:p
Peroxydisulfuric acid
Peroxymonosulfuric acid
due to the ability of the sulfur atom to share electrons with oxygen and with other sulfur atoms, as is illustrated by the structural formulas of a number of these acids given above. The behavior of sulfur is somewhat comparable tc carbon in this tendency to form molecules of high molecular weight with oxygen and hydrogen. A few of the more important acids will be discussed.
24.
acid
is
2H 2SO 3 + Zn = ZnS O4 + 2H
2
Hyposulfurous Acid. The zinc salt of hyposulfurous formed by the reduction of sulfurous acid by zinc:
2
O.
A solution of the sodium
262
REFERENCE
[Ch. XII
addition of sodium
prepared commercially from the zinc salt by the sulfite, as zinc sulfite is but moderately soluble. The salts are also prepared by the cathode reduction of bisulfite solution 2H 2 SO 3 + 2e~ = S 2 O 4 + 2H 2 O.
salt is
:
The
is too unstable to be prepared in the pure state. a very rapid reducing agent, reducing oxygen almost ~ instantaneously, 2H 2 O + HS 2 O 4 = 2H 2 SO 3 + H+ + 2e~,
acid
It is
0.23 volt. The sodium salt is employed commercially for the reduction of indigo to indigo white. 26. Thiosulfuric Acid. Sulfites react with sulfur in alka-
form thiosulfate: S0 3 + S = S 2 O 3 ~~. The free acid is unstable and the reaction is reversed by acid, sulfurous acid being formed and the sulfur precipitated. The reversal may be brought about even by weak acids: thus a sodium thiosulfate solution becomes turbid if exline solution to
~~
posed to the action of the carbonic acid of the

sulfur precipitated
loidal.
is
air.
The
amorphous and at first usually colThe somewhat analogous oxidation of sulfide by

is
,
discussed under the polysulfides. The product of that oxidation, SS4 may be considered as the tetrathiosulfate.
sulfur in alkaline solution
Thiosulfate
volt)
is
oxidized (2S 2 O 3
= S 4O
2er,
0.15
by
iodine, ferric ion,
and other moderately strong
oxidizing agents to the tetrathionate. This extremely important reaction with iodine is discussed under that ele-
More powerful oxidizing agents, such (cf. X 21). as chlorine and bromine, oxidize the thiosulfate to sulfate:
ment
2
8C1- + 10H+. Thiowith many of the ions " of the more noble metals, including Ag 4 Au" 4", Cu + r Hg++, Pb++ Advantage is taken of this property in pho" tography in the fixing bath," to dissolve out the unchanged silver bromide. Sodium thiosulfate, Na 2 S 2 O 3 -5H 2 O, called "hypo" from the older name "hyposulfite," is of considerable commer2
SH O + S O 3
4C1 2
= 2SO4
sulfate forms
complex ions and
salts
"
",
cial
importance.
Besides
its
use in photography,
it is
em-
27]
GROUP
VI.
263
ployed in the textile and paper industries as an "antichlor" to remove the excess chlorine used in bleaching, and in certain metallurgical processes. The very unstable sulSO 2 has the same oxidation state as the 2 foxylic acid,
-
average value for the sulfur in thiosulfate and decomposes to give the latter,
2H SO 2 =
2
S 2O 3
+HO
2
Soluble sulfides readily dissolve sul26. Polysulfides. ~" fur to form a series of compounds giving the ions, S 2 to S6 The alkaline solutions may be evaporated and the
.
crystalline salts obtained, but the acids are unstable, forming hydrogen sulfide and free sulfur. These polysulfides act both as reducing and oxidizing agents. An example of the
latter action
is
the oxidation of stannous sulfide to thio-
polysulfide, made by dissolving sulfur in lime, the product thereby containing some thionic salts, is used extensively as an insecticide for vineyards and
stannate.
Calcium
orchards.
27. Thionic Acids.
The
structural formulas of a
number
have been indicated above. of acids of the type, 6 2 Sn The subscript varies from 2 to 5. These acids are analogous
,
to the peroxyacids. Thus tetrathionic acid may be preby the anodic oxidation of thiosulfate, 2HS 2 Oa"~ pared
2e~, similarly to the preparation of peroxyand the structure disulfuric acid, 2S 2 8 from sulfuric acid
2
4 6
H SO +
of the tetrathionate differs from that of persulfate only by the substitution of sulfur for the peroxygen. Dithionate
may be = S2O
6
prepared by the anodic oxidation of sulfite, 2SO3 + 2e~. Mixtures of the acids result from the
2 2
interaction of sulfurous and hydrosulfuric acid in solution:
3H
2S
+ 3SO = H S O 2H S + 6SO - H S O + H S O + 9SO = H S O + 2H S O The gases themselves

4
6
;
6.
react to form sulfur and water. The various acids or salts are formed as intermediate products in many oxidation-
264
REFERENCE
[Ch. XII
reduction reactions involving sulfates and sulfites: thus, manganese dioxide reacts upon cold sulfurous acid to form
manganese dithionate
MnO + 2H SO = MnS O + 2H
2
O.
The
acids are unstable in regard to decompositions giving sulfate, sulfite, and sulfur. The tetrathionate is the most
important of these compounds.

sulfate
by
the action of iodine
formation from thioand ferric ion has been disIts
cussed.
important acids and an peroxyoxygen are known. The oxide, SO 4 or SOa-SO^ is formed in small amounts by an electrical discharge in a mixture of sulfur dioxide and
28. Peroxysulfuric Acid.
Two
oxide of sulfur containing
oxygen:
SO 2
+ O = SO
2
4.
When
dissolved
in
dilute
sulfuric acid it does not give the ordinary peroxide reactions. Persulfuric acid, H 2 S 2 Og may be prepared by the reaction between cold concentrated sulfuric acid and conH 2 O 2 = H 2 S 2 O8 centrated hydrogen peroxide: 2H 2 SO 4 of cold concentrated sulfuric 2H 2 O, or by the electrolysis
acid:
2HSO ~ = H
4
S 2 O8
2e~~.
The sodium
salt is pre-
pared commercially by the electrolysis of concentrated

solution
disulfate
of
is
sodium acid
sulfate.
The sodium peroxy-
but moderately soluble and crystallizes out.
Peroxydisulfuric acid hydrolyzes in steps forming first the peroxymono-acid called "Caro's acid," and this hydrolyzes
to
form sulfuric acid and hydrogen peroxide:

2
S
2
8
4
+ H +HO
2
= H SO
2
+ H SO
2
H SO + H O = H SO
2 5 2
2.
The mono-acid may be prepared by
the elec-
trolysis of cold moderately concentrated sulfuric acid. Both of the acids evolve oxygen readily, but their salts are
fairly stable. The sodium peroxydisulfate is of considerable commercial importance as an oxidizing agent
:
2SO 4
= S2 O 8
2e~
-2.05 volts
In the presence of Ag+ as a catalyst, manganous ion is oxidized to permanganate by the acid. The action of silver
32]
GROUP
VI.
265
as a catalyst appears to involve the formation of
AgO+
and Ag++. 29. Other Thio-acids. Sulfur may be substituted for in a number of acid radicals similar to its substioxygen
tution in the sulfate radical, provided the radical is not such a powerful oxidizing agent that the sulfur is rapidly oxidized to higher valences. For example, compounds are prepared in which the oxygen in phosphate is replaced by sulfur, forming the series, Na 3 PO 3 S to Na 3 PS 4 The strong analogy between sulfur and oxygen is well illustrated by the reaction of barium sulfide and carbon disulfide to give
.
barium thiocarbonate, BaS + CS 2 = BaCS 3 similar to the formation of barium carbonate from the two oxides. Men,
tion should also be
many
(cf.
made of thiocyanic acid, HSCN, as of the salts of that acid are of considerable importance
Sulfur
tri-
XIII 26). 30. Sulfur Trioxide-ammonia Derivatives.
oxide and
ammonia
2
react
3
to
form amidosulfonic acid
(sulfamic acid),
.
NH SO H
The former is (SO 3 H) 2 with concentrated sulfuric acid. Sulfamic acid is used in the manufacture of dyes and cleaning compounds and in
tanning.
textiles.
and amidodisulfonic acid, NHalso formed by heating urea
Its salts are valuable in flameproofing
paper and
Sulfamide,
of
ammonia on
31.
SO (NH 2 )2, is sulfuryl chloride, SO

2
formed by the action

2
C1 2
Other Acids of Selenium and Tellurium. The tendency to form long chain complicated acids, and the tendency
to substitute for oxygen, exhibited by sulfur in the thioacids, decrease with the heavier elements in the group. Both selenium and tellurium form salts of polyhydro acids, Selenium forms an unstable peroxye.g. NaSe 2 NaTe 3
,
acid but tellurium does not. Selenium substitutes for oxygen in a number of acids and in many organic compounds,
e.g.,
NaSeCN, sodium
selenocyanate.
The halogens combine with the elements sulfur, selenium, and tellurium to form nu32.
Halogen Compounds.
266
REFERENCE
[Ch. XII
merous compounds. These, together with a number of oxycompounds containing chlorine with oxygen and hydrogen, have been summarized in Table VI.
chlorides,
TABLE
VI
HALIDE AND OXYHALIDES OF GROUP VI
In general, the halogen compounds hydrolyze with water to form the hydrogen halide and the acid of the positive element. The latter may, however, be unstable in respect
to decomposition into
oxidation states.
rate of hydrolysis
compounds of higher and lower In some cases, as for example SF 6 the

,
extremely slow. The most important of these compounds is sulfur monoThis is formed by the direct action of chloride, S 2 C1 2 hot sulfur. It is a reddish yellow liquid and chlorine upon an excellent solvent for sulfur. For this reason, it is used It is hydrolyzed by water: 2S 2 C1 2 in vulcanizing rubber. 2H 2 O = SO 2 + 4HC1 + 3S. The other two chlorides may be formed by the action of chlorine upon cold monochloride, but are decomposed by gentle heating.
is
.
The compound S 2 Fi
is
formed
in small
amounts together
34]
GROUP
VI.
267
with
SF 6 when
sulfur
is
burned
in fluorine.
It is
highly
Iodine does essentially non-toxic. not react with solid sulfur or selenium, but in a solution of ethylene bromide, iodine reacts with selenium to form
6
toxic while the
SF
is
both 862! 2 and Sel4.

Sulfur dioxide reacts with chlorine, forming sulfuryl Thionyl chloride, SOC1 2 results from the chloride, SO 2 C1 2 reduction of phosphorus pcntachloride by sulfur dioxide:
.
,
PC1 5
+
3
SO 2 = SOC1
POC1 3
Chlorsulfonic
acid,
formed by the direct union of sulfur trioxide C1, and hydrogen chloride. Fluosulfonic acid may be prepared by the analogous reactions or by the action of conis
HSO
centrated sulfuric acid upon calcium fluoride. It reacts The ammonium salt reacts with boric acid to form BF 3 with ammonia to form ammonium sulfamate, 4 SO 3 2 Pyrosulfuryl chloride, S 2 O 6 C1 2 is formed by the direct union of sulfur trioxide and sulfuryl chloride. 33. Selenium and Tellurium with Sulfur. There appear and sulfur only, to be no compounds containing selenium and the two elements form several series of mixed crystals. The precipitate obtained by passing hydrogen sulfide into tellurous acid appears to be a mixture of the free elements
.
NH
NH
and the
sulfide
TeS 2
Concentrated sulfuric acid dissolves both selenium and tellurium with the formation of the compounds, SeSO 3 and TeSO 3 respectively, analogous to S 2 O 3 (Par. 11). Selenium may be substituted for sulfur in certain of the
,
complex sulfur
nized
34. Analytical.
2 SSeO 3 acids, e.g. seleno sulfuric acid, Sulfur. The free element may be recog.
;
by the pungent odor of sulfur dioxide upon burning or by dissolving in hot alkali solution and placing a drop of the
solution on a silver coin, a black stain, Ag 2 S, indicating the presence of sulfur. Sulfides are detected by the liberation
which may be recognized moist lead acetate paper. by its odor, or by its reaction with Sulfates are detected by the precipitation of barium sulfate,
of
hydrogen
sulfide
by dilute
acids,
268
REFERENCE
is
[Ch. XII
which
not soluble in dilute acids.

is
Since sulfur in the lower
valences
readily oxidized to sulfate, this also constitutes a general method for the detection and estimation of sulfur. Thus in quantitative analysis, sulfur is usually precipitated and weighed as barium sulfate. Due to the occlusion of
soluble salts
by the barium sulfate, it is difficult to obtain the precipitate pure. This error is decreased by precipitating from a large volume, since the occlusion is proportional to the concentration of the soluble salts, and also by digesting the precipitate for some time, which allows the more soluble small crystals to dissolve and slowly recrystallize out on the larger crystals. If precipitated from cold con-
centrated solution, barium sulfate it cannot be retained by ordinary
is
so finely dispersed that
filter
paper.
.
element dissolves in concentrated sulfuric acid to form a green solution, SeSO 3 In the ordinary scheme of analyses, selenates are precipitated by hydrogen sulfide as elementary selenium, which is soluble in ammonium polysulfide. Red selenium is precipitated from
Selenium.
free
The
cool
selenous acid solution
hydroxylamine hydrochloride, NH 2 OHHC1, being often employed. The precipitate turns black upon heating. A separation of selenium, arsenic, and germanium from the
other elements
solution with
by strong reducing
agents,
may be made by distilling the material in HBr and Br The distillate consists of SeBr 4
2.
, .
and GeBr 4 3 AsO 4

,
In quantitative analysis, the selenium may be precipitated and weighed as the element, or determined volumetrically with oxidizing or reducing agents through the
selenous-selenic acid couple.
Tellurium. Tellurium resembles selenium in its precipitaThe two elements may be tion with hydrogen sulfide. by the hydrogen bromide treatment (cf. above) separated
or by the reactions of the tetrapositive acids with iodide in dilute acid, selenium precipitating as the red element, and tellurium forming a back precipitate, TeI 4 soluble in ex,
35]
GROUP
VI.
SULFUR, SELENIUM, TELLURIUM
269
. cess iodide to give a red solution of TeI 6 Tellurium may be weighed quantitatively as the metal or the dioxide.
Tellurous acid
may
be oxidized by permanganate quantita-
tively to telluric acid.

35. Polonium. Isotopes of element number 84 occur in the various disintegration series (cf. XXIII). The name polonium was first given to the isotope of mass 210 in the
uranium series which has a half-life of 138 days. Polonium forms the hydrogen compound H 2 P, but
it is
than the corresponding compound with the lighter elements of the family and is readily oxidized:
less stable
much
Po = Po
to
2H+
2e~\
>
"
.
1.0
volt.
The
ion
Po++
be stable in acid solutions although some appears " It is a moderately powerful authorities claim it is Po^4 4
oxidizing agent,
Po = Po++
2e;
0.65 volt.
Metallic
++ 2H 2 O = PoO 2 precipitated as the dioxide Po0 2 Po + 4H Powerful oxidizing agents 0.8 volt. 2e~\ ca form PoOs. The dioxide is somewhat acidic, probably
,
polonium plates out on a strip of tin placed in a solution of 2 ion. the Upon anodic oxidation the element is
probably of the ion also appears to The complex chloride PoCl 6 PoO 3 be stable. Polonium is precipitated by hydrogen sulfide, probably as PoS.
dissolves in
.
OH~~ and forms
salts,
36.
Summary
1.23
of
Group
Potentials.
The
following po-
tential
diagrams are given to summarize the group.
HO
2
O2
0.14
0.50
S 2O 3
0.38
0.20
2S
S
0.35
H SO
2
SO 4
SeO 4
Se
0.74
1.15
H
H
Se
0.69
H
0.53
ScO 3
~
6 ( 8)
~
TeO 2(S
)
1.02
Te
Te
H TeO
6
>
2
1.0
ca
0.65
ca
0.8
Po0 2(8
)
1.3
Po
Po
Po++
Po0 3(s)
Chapter XIII
CARBON
1. Several hundred thousand compounds of carbon are known, and the properties and reactions of these compounds constitute such a large portion of chemical knowledge that the whole of the science is now generally considered in respect to two great subdivisions, organic chemistry dealing with the carbon compounds, and inorganic chemistry dealing with the compounds of all the other elements. It was once felt that the structure of the carbon compounds differed in some fundamental respect from that of the compounds of other elements, but it is now realized
that their constitution can be correlated with the structure of the carbon atom and with the same general principles of
compound formation which have been
discussed in connec-
tion with the other periodic groups. This chapter will deal briefly with the structure of organic compounds in general
and with the properties of the oxides and simpler carbon compounds. The relation of carbon to the other members of Group IV will be considered in the two subsequent
chapters. 2. Structure of
Carbon Compounds. Carbon forms com4 to pounds in which the oxidation state varies from + 4. However, the assignment of oxidation states in most of its compounds is so arbitrary as to be of little significance,
is, although we know the total number of valence electrons in the molecule, we are unable to say that a given number of electrons are definitely associated with a 270
that
2]
CARBON
271
The carbon atom, having four electrons, a position intermediate to the elements which, occupies on one side, lose their electrons to form positive ions, and on the other side add electrons to complete the octet and thus form negative ions. As a consequence of this position,
certain atom.
appears to complete the In terms by sharing of the idea that the pair of electrons constitutes a chemical bond, the behavior of carbon may be summarized by the statement: carbon tends to form compounds in which it shares four pairs of electrons with the surrounding atoms. The four bonds are arranged in tetrahedral symmetry, the carbon atom being at the center and the four attached
it
forms compounds in which

its
it
octet
electrons with other atoms.
atoms at the corners of the tetrahedron. As an illustration of this statement and of the non-polar character of the
bonds, the electron formulas of the simple carbon, hydrogen, chlorine compounds are given below (cf. also Hildebrand, Prin. of Chem., p. 90). Oxidation State:
-4 H H
:
2
:
+2
Cl
: :
-M
:
:
Cl
Cl
H H
ci
Cl
C
Cl
Cl
Cl
C
Cl
Cl
This idea of the four bonds of carbon has been of the

greatest importance in the development of organic chemistry, and it is customary to represent these bonds by lines,
e.g.,
H
H C H H
If
one of the attached atoms
is
divalent, this
is
represented
272
REFERENCE

to
it, e.g.,
[Ch. XIII
by drawing two bonds
H-i:=o
All of the carbon bonds are non-polar in nature, and in general the bond energies are so large that dissociation into ions does not take place. The most important conse-
quence of the non-polar bonds chain carbon molecules, e.g.,
is
the formation of long
H H H H H C C C C H
A
and
of complicated
Ui
compounds
of very high molecular
weight containing hundreds of atoms. Such compounds constitute plant and animal tissues; from which fact, the term organic chemistry has arisen. Several types of compounds are formed in which the concept of the four bonds can only be kept by placing two or more of them between adjacent carbon atoms, e.g.,
H H
H C=C H
Such compounds are
"electron pairs" such
and
H C=C H
In terms of the
called "unsaturated."
compounds would be written as
H H
The
:
H
:
and
tetrahedral picture postulates that, in the single
bond two tetrahedra are attached by a corner, in the double bond by an edge and in the triple bond by a face. Bond angles have been determined for a number of unsaturated molecules and in most cases, the values are in approximate
agreement with the tetrahedral structure.
3]
CARBON
273
electron formulas preserve the idea that carbon always has four bonds, but other electron arrangements must at least be considered as possible, e.g.,
The
H H
H
:
and
C
ii
It will be observed that the fundamental difference between saturated and unsaturated carbon compounds is that the
complete all of the octets, resonance between the various electron structures so that no one formula can be written which In carcompletely represents the state of the molecule. bonates, such as calcium carbonate, CaCOs, the solid is built up of a lattice of calcium and carbonate ions, and the carbonate ion has the three oxygen atoms arranged symmetrically about the carbon in the same plane:
latter lack sufficient electrons to
and there doubtless
is
:0
:6 :c" :0
This is a definite example of a compound in which the carbon atom does not have tetrahedral symmetry and the idea of the four bonds can only be preserved by assuming a double bond between one oxygen and the carbon, and in order to give the observed triangular symmetry this double bond must resonate around the molecule. 3. Occurrence of Carbon. Carbon occurs free in the forms of diamond and graphite. Coal is largely crystalline
amorphous carbon, although it contains many complex compounds of carbon with hydrogen, as well as with oxygen and nitrogen. Methane, CH 4 is the principal constituent of natural gas; and heavier hydrocarbons constitute the mineral oils. The element is found most abundantly in the
,
form of metal carbonates, limestone, or calcium carbonate,
274
REFERENCE
[Ch. XIII
constituting one of the most common minerals. The occurrence of carbon in all animal and plant tissue has been
mentioned.
Elementary Carbon. Many of the physical properdiamond and graphite may be correlated with their crystal structures. The diamond crystal is cubic and each carbon atom is surrounded by four other atoms located at
4.
ties of
the corners of a regular tetrahedron (Append. V). The four carbon valences are thus satisfied by carbon atoms, and
the crystal is held together by bonds which are essentially the same as in the carbon compounds. As a result, diamond is the hardest known substance, and its melting
point
is
probably higher than that of any other element.
bonds between the atoms, and the crystal is, therefore, a nonconductor of electricity. Diamond has a very high index of refraction, 2.42; and this gives the cut gems a high brilliance, as most of the light falling upon them is totally reflected from the interior surfaces. Graphite possesses hexagonal symmetry, and crystal structure data indicate planes of carbon atoms in hexagAll of the electrons are doubtless held in the
*5T
*T
onal
rings.
Graphite
soft,
is
remarkably
and the
crystal readily splits off thin flakes. The cleavage
carbon atoms of the crysGraphite 8 an elec . trical conductor, although only one thousandth as good as copper. This fact is in harmony with the crystal structure in that not all of the carbon bonds are satisfied, and some of the electrons are thus free to move through the crystal. All forms of carbon are somewhat volatile at 3500, and the vapor, upon condensing, forms graphite. Although the experimental data are somewhat uncertain, the most reFIG.
1.
planes doubtless are identical with the planes of the
Crystal structure of graphite.
4]
CARBON
275
combustion lead to the value: CD = C it may be calculated from this value that diamond at one atmosphere pressure is unstable at all
liable heats of
220
cal.;
and
temperatures in respect to graphite. However, diamond is denser than graphite and under 8000 atmospheres at 25 it would become the stable form. Experimentally, it is to convert diamond into graphite by heating. possible Moissan claimed to have prepared small diamonds by quenching solutions of carbon in molten metals. Naturally occurring diamonds have been crystallized from solutions of molten magnesium silicates under conditions of high pressure. Carbon is soluble in the basic silicates but if free
SiC>2 is present, it oxidizes the
' *
carbon.
This
is
the reason
diamonds occur only in basic silicates. The so-called amorphous carbon," such as charcoal, appears upon examination by X-rays to resemble graphite
in structure, except that it is highly
Upon
oxidation
porous or cellular. hot nitric acid and potassium chlorate, by

,
both charcoal and graphite yield mellitic acid, C 6 (CO 2 H) 6 a derivative of benzene, thus indicating the ring structure Charcoal of the carbon in these substances (Par. 16).
possesses the property of absorbing gas, and, when cooled in liquid air, will absorb air from a sealed tube to produce
a
is
vacuum
of 10~5
mm., or
better.
Highly active charcoal
used in gas masks for the absorption of poison vapors. The activation is carried out by heating for long periods in steam, which serves to remove adsorbed hydrocarbons from the surface. One cc. of active charcoal is said to have a
Bone charcoal is surface of about 1,000 square meters. used in sugar refining to absorb coloring matter present in the crude sugar. Other amorphous forms of carbon are lamp black and carbon black. The former is made by the incomplete combustion of hydrocarbon oils and the latter
by impinging the flame of natural gas upon a metal surface. Both are used as pigments in ink, but the carbon black is now far more important. Its largest use is in compounding
276
REFERENCE
[Ch.
XNI
rubber for automobile tires. In 1946 almost five hundred billion cubic feet of natural gas was consumed in the United States in the production of over a billion pounds of carbon
black.
lead pencils.
Falls
Graphite has long been used for the manufacture of It is obtained from mines in Ceylon and
is
Madagascar, and
Because of
now made in large quantities at Niagara

coal in an electric furnace.
by heating anthracite
used in making crucibles for presence of a small portion of clay greatly increases its resistance to oxidation. Because of its high melting point, graphite is extensively used for
its infusibility, it is
use at high temperatures.
The
electrodes in electric furnaces.

is
Graphite, or gas carbon,
also used in arc
lamp
electrodes, cerium fluoride being
often added to provide a metal vapor which increases the brilliance of the arc and also reduces its resistance. Ground
in oil or
ite
water with tannin or other suspending agent, graphforms a stable suspension, which is used in lubricating
Graphite is also employed extensively in prometal surfaces from oxidation, e.g. in stove polish. tecting Liquid potassium is absorbed by graphite. The alkali atoms apparently enter the crystal between the planes of carbon atoms. Two definite compounds, C 8 K and Ci 6 K, Powerful oxidizing agents form so-called are formed.
bearings.
Here again the oxygen atoms enter the between the carbon planes. The composition of the crystal product varies from a ratio of oxygen to carbon of 1 to ~ In a similar manner HSO 4 groups enter the 2.9-3.5. crystal when graphite is treated with sulfuric acid in the
graphitic oxide.
presence of a strong oxidizing agent. The product is known as blue graphite, and when treated with water, graphite is again /ormed. A technical process for the purification of graphite is based on this fact. Fluorine also enters the graphite crystal, forming the explosive carbon monofluoride.
As
sults in a considerable increase in the
in the other absorption reactions the process revolume of the crvstal

,
5]
CARBON
TABLE
I
277
ATOMIC AND PHYSICAL PROPERTIES OF CARBON

Atomic weight Atomic number
Isotopes Electrons in various quanturn levels, 1st
12.010
6 12,13
2
lonization potential in volts, 1st electron 2d electron 3d electron 4th electron
11.2 24.3 47.6 64.2
2d
Density
D G
3.51
Melting point, Boiling point,
C C
"...
G
D
3500 4830
Heat
of sublimation kcal.
2.25 170.4
Electrical resistivity,
ohm-cm
5 1.4
X 10 X 10-*
14
The radioactive isotope of carbon with mass 14 occurs in nature as the product of the reaction between cosmic-ray n = C 14 It has a halfneutrons and nitrogen, N 14 p. 14 life of 5720 years and is transformed to by a 0-emission. The isotope appears to be uniformly distributed in atmospheric carbon dioxide and the carbon in living material
+ N
gives an average 12.5 /3-disintegration per minute per gram of carbon. This offers a means of dating carbon containing
material which was removed from the equilibrium process in ancient times. Thus wood samples from old Egyptian
tombs gave a specific carbon activity of 7 counts ment with the age of the tombs and predicted rate
in agree-
of decay.
produced in the high-flux neutron reactors and has become extremely important as a "tracer," used to
is
14
also
follow the course of organic reactions.
OXIDES AND ACIDS

5. Carbon forms the monoxide, CO, which is the anhydride of carbonous or formic acid, HCO2H, and the dioxide, CO 2 which is the anhydride of carbonic acid, 2 CO 3 In
,
addition, several anhydrides of more complicated organic acids are known: e.g., carbon suboxide, CaO2, the anhydride
of malonic acid,
CH (COOH)
2
2.
remarkably similar to nitrogen in physical properties (Table II). The two gases have the same molecular weight and also the same number (10) of
is
Carbon monoxide
278
REFERENCE

TABLE
II
[Ch. Xlll
PROPERTIES OF CARBON MONOXIDE AND NITROGEN
valence electrons. It seems probable from the similarity in properties that the arrangement of the electrons in both molecules may be the same. Probably no single electron structure should be written but rather a number of structures such as,
:
or
or
C O
:
with
resonance between them.
Carbon monoxide is but slightly soluble in water, 3 cc. per 100 cc. of water at 8. It is moie soluble in alkalies, giving
formates:
CO + NaOH = HCOONa. The

:
gas
is
readily
prepared in the laboratory by the action of sulfuric acid = formic or oxalic acid, or ferrocyanide (1)
2
2
2
on
6
HCOOH CO + H O, (2) H C O = CO + CO + H O, (3) K Fe(CN) + 6H SO + 6H O = 6CO + 2K SO + 3(NH SO + FeSO The formation from reactions involving carbon,
4
2 2
4) 2
4.
oxygen, and water
is
discussed in later paragraphs.
Carbon monoxide reacts with many metals, forming carK6 (CO) 6 Ni(CO) 4 Co 2 (CO) 8 bonyls, e.g., Fe(CO) 6 Cr(CO) 6 W(CO) 6 Ru(CO) 5 Mo(CO) 6 The nickel compound is of especial importance (rf. XIX 18). Iron and cobalt form the unusual carbonyl hydrides Fe(CO) 4 H 2 The so-called potassium (cf. XIX 16) and Co(CO) 4 H. to be a derivative of hexahydroxy carbonyl appears The oxide enters into a number of benzene, C 6 (OK) 6 M "coordination complex ions such as K 3 Fe(CN) 6 CO; and the gas is absorbed by both acid and ammonical solutions
,
,
,
of cuprous chloride with the formation of rather unstable
complexes, possibly
solutions are
~ Cu(CO)Cl 2 and Cu(CO)NH 3+. Such
employed
in gas analysis in the estimation of
6]
CARBON
279
carbon monoxide, although small amounts of the gas are more accurately determined by passing the gas over hot (160) iodine pentoxide: SCO + I 2 O 6 = 5CO 2 + I 2 The iodine is absorbed in iodide solution and titrated with
.
thiosulfate.
directly with chlorine in the or in the presence of active charcoal as a catalyst sunlight, to form phosgene, carbonyl chloride, COC1 2 The reaction is highly exothermic, and is, therefore, favored by low
.
Carbon monoxide unites
temperatures (below 350). Carbon monoxide is extremely poisonous. Air containing 1 part in 2000 will cause death in about four hours; and 1 part in 100 will cause death in a few minutes. The action is due to the formation of a bright physiological red compound with the haemoglobin of the blood. Gas masks to protect against carbon monoxide contain a mixture of manganese and copper oxides known as "hopcalite," which acts as a catalyst for the oxidation of the gas. 6. Equilibria Involving Carbon Monoxide and Dioxide. Around 500 C., carbon (in excess), in an atmosphere of oxygen, gives almost completely carbon dioxide: C + O 2 = CO 2 (1), but at 1000, the reaction (with excess carbon) gives almost pure carbon monoxide: 2C + O 2 = 2CO (2).
CO 2 = 2CO (3), that in the equilibrium: C high temperature favors the formation of the lower oxide. Data on the equilibrium are given in Table III.
It follows
C(graph)
TABLE III + CO = 2CO

2
At low temperatures, carbon monoxide
is
unstable with
respect to the decomposition (3) above, but the rate of decomposition is extremely slow; however, around 300 platinum or nickel act as efficient catalysts.
280
REFERENCE
[Ch. XIII
With
excess oxygen, both carbon and carbon monoxide
are oxidized to the dioxide:
2CO
is
+ O = 2CO
2
(4).
Only
at extremely high temperatures reaction (4) reversed and The union of carbon dioxide dissociated (Table IV).
carbon monoxide and oxygen is slow at low temperatures, and even at high temperatures, if the gases are perfectly
dry.
Water, therefore, appears to act as a catalyst.
= CO 2 O(g) 2 (5) is very equilibrium: C important in the manufacture of artificial fuel gas (see
The
+H
1
;
+H
is
below).
At 25, the equilibrium constant

it is
about 10~ 16
hence there is a rapid change in the direction of the reaction with temperature. Below 500, steam will oxidize carbon monoxide: CO H 2 (g) = CO 2 H 2 (6). This reaction is utilized in the preparation of commercial hydrogen from water gas (Par. 7). Data on the equilibrium are given in Table V.
but at 600
about
TABLE V CO + H (K - C02 + H
2
)
In the
hydrogen and alcohols, or other oxidation products of hydrocarbons,

for example,
will
presence of catalysts, carbon monoxide and combine to form a number of hydrocarbons
CO + 3H = CH + H O CO + 2H = CH OH 12CO + 3H = C H + 6CO 2
2 4
7J
CARBON
281
reactions, the most important commercially is the formation of methyl alcohol, CH 3 OH, or methanoL The reaction is favored by pressure (100-200 atmospheres are used), and the temperature range is between 300 and 600 C. Various mixed metal oxides are employed as Zinc oxide favors the formation of methanol, catalysts. while cobalt metal with chromium oxide yields hydrocarbons. Methanol is important as a solvent, and as a raw material for the synthesis of many organic compounds. It is a very satisfactory fuel for gas engines. The frequent mention of carbon monoxide in metallurgical processes arises
Of these
through
its
powerful reducing power,
which enables
it
to
2
CuO + CO = CO
tion of carbides.
7.
remove oxygen from metal oxides: e.g., + Cu (7). The more noble the metal,
the greater the tendency for reaction (7) to take place. In certain cases, the reaction is complicated by the forma-
Carbon Monoxide Fuels,
Carbon monoxide
is
an
important constituent of several artificial fuels. When a limited supply of air is passed through coke or anthracite
coal, the resulting
mixture
is
known
as producer gas,
and
contains carbon monoxide (30 to 40 per cent), nitrogen (60 per cent), and hydrogen (2 to 5 per cent). A gas of somewhat similar composition, called blast furnace gas, is a
product of iron smelting. The most important artificial gas, however, is water gas, made by passing steam over hot coal. The reaction is endothermic (see reaction (5) above) and in order to maintain the required temperature (around 600), it is necessary to turn off the steam every few minutes and blow air in for a brief period. The resultant mixture of gases consists of carbon monoxide (40 to 50 per cent), hydrogen (45 to 50 per cent), carbon dioxide
and nitrogen (4 to 5 per cent). In certain where crude oil is cheap and coal expensive, oilwater gas, for cooking and heating, is made by spraying crude oil and steam upon heated bricks. The heavy hydro(3 to 7 per cent),
localities
,282
REFERENCE
[Ch. XIII
carbons are "cracked" by the heat into carbon and lighter gases, such as CH 4 and C 2 H 6 the former reacts with the steam to form carbon monoxide and hydrogen.
;
8.
Formic or Carbonous Acid.
Carbon monoxide reacts

:
with alkalies, producing formates, but does not react with water at ordinary temperatures. However, the equilibrium CO + H 2 O = HCO 2 H is attainable at 150 in the presence of hydrogen chloride with the system under pressure; and from measurements of this equilibrium, it may be calculated that formic acid is stable at room temperature with respect to carbon monoxide at one atmosphere. Sulfuric acid readily removes the water from formic eicicl and evolves carbon monoxide. Formic acid has the formula,
H C OH
II
and not
H O C-O H
O
In this respect, where in the
it
1
is
and
similar to the acids of phosphorus 3 states the shifts to the P.
is monobasic, and the dissociation constant is The acid has a pungent, irritating odor, and 10~4 All of the formates blisters the skin like a nettle sting. are soluble, but the silver and lead salts only moderately. The product of the oxidation of 9. Carbon Dioxide. free or combined, with excess of oxygen is the carbon, This oxide is also formed by the action of dioxide, CO 2 H 2 SO 4 = CaSO 4 acids upon carbonates: CaCO 3 2O
The
1.8
acid
+H
by the thermal decomposition of carbonates or CO 2 An important combicarbonates: MgCO 3 = MgO mercial source of the oxide is the alcoholic fermentation of
2
;
+ CO
or
sugars:
C H 12 O = 2C H OH
6 6 2
6
+ 2CO
2.
atmosphere in amounts from 3 parts in 10,000 in the country, to 1 part in varying 100 in crowded and poorly ventilated rooms. It also occurs in effervescent mineral waters, and issues from the ground
Carbon dioxide occurs
in the
9]
CARBON
283
in large quantities in certain localities, as the Valley of
Death, in Java. Solid carbon dioxide has a vapor pressure of

at
If
1 atmosphere and therefore sublimes at that temperature. 78.5, heated under pressure, it
melts at
atm.
56
(5.3 atm.).
90
The
temperature of the liquid is 31.35, the critical pressure, 73 atmoscritical
80
The pheres. sure at 20
vapor presis 59 atmospheres. The oxide is usually handled commercially as the liquid in steel
If the liquid is cylinders. allowed to flow from the
70
60
60
cylinder into a heavy cloth bag, the heat of vaporization

is sufficient
12345
FIG.
2.
6Spc.Volume
to cool a
Pressure- volume curves for CC>2.
large fraction of the oxide to the solid state, foiming carbon solution of the solid in acetone under redioxide snow.
duced pressure may be employed to obtain temperatures 110. around The solubility of carbon dioxide in water at 1 atm. pressure and various temperatures is:
to about 5 atmospheres, the solubility is nearly proportional to the pressure, following Henry's law, but above that
Up
pressure the solubility becomes greater due to the formation of carbonic acid. Soda water contains carbon dioxide under a pressure of 3 to 4 atmospheres. The rate of the
slow requiring an activation energy of about 19 kcal. In the lungs the reaction is catalyzed by the enzvme, carbonic anhydrase.
reaction,
2
CO + H O = H CO
2 2
is fairly
284
REFERENCE
electron

structure
is
[Ch. XIII
The
:
generally
is
written
as
but there probably

:
resonance with other
structures, e.g.,
O C
:
Carbon dioxide is not poisonous; its harmful effects are due rather to suffocation through lack of oxygen. Air containing 2 to 3 per cent of the gas may be breathed without apparent ill effect, but above 5 per cent panting is produced and 50 per cent carbon dioxide can be tolerated only for a short time. The high humidity of badly ventilated rooms is probably more harmful than the carbon dioxide content. The principal use of carbon dioxide is in the preparation of carbonated beverages. Liquid carbon dioxide is used in
;
refrigeration cycles; the solid is used in cold storage, in place of ice, especially in shipping fruit, as the gas liberated
tends to prevent the development of aerobic bacteria. The gas is employed in the manufacture of certain carbonates, including the sodium carbonates and white lead. Carbon dioxide is generated in the soda-sulfuric acid type of fire extinguisher. In other types of extinguisher liquid carbon
few per cent of dioxide under pressure is employed. carbon dioxide in air will render it a non-supporter of combustion of most carbonaceous material. highly elec-
tropositive element like in pure carbon dioxide.
magnesium
will
continue to burn
Carbon dioxide is absorbed from the atmosphere by plants, and is the source of the cellulose in plant tissue: 6CO 2 + 5H 2 O = C 6 HioO 6 + 6O 2 This reaction (or related
.
reactions) requires the absorption of energy this is supplied by sunlight through the agency of the chlorophyll. The mechanism of the reaction is much more complicated than
;
the overall equation indicates. Some carbon dioxide is absorbed in the dark but the regeneration of the active re-
ducing agent requires

tion
light.
It is this
absorption of radia-
by plants, that renders the sun's energy available to us through the use of plants as food, and of plant prod-
10J
CARBON
wood,
coal,
etc.,
285
ucts,
as fuel.
The decomposition
of
plant tissue,
of
atmosphere, and
of carbon dioxide
course, returns carbon dioxide to the this continuous absorption and evolution
by plants
is
sometimes referred to as the
carbon cycle. 10. Carbonic Acid. The structure of carbonic acid has been discussed (Par. 2). The acid is known only in solution, in which it doubtless exists as the meta- rather than
the ortho-form. At 1 atmosphere of CO 2 and 25 C., a water solution contains 0.0338M H 2 CO 3 The acid is weak,
.
the dissociation constants being, respectively: KI = 4.3 = 4.7 10~ u A saturated solution (1 2 10-*, and
4 H+ These constants are atm.) thus contains 1.2 X 10~ correctly used with the assumption that all of the CO 2 is present as H 2 CO3. However, there is evidence that less than one per cent of the CO 2 is in the acid form and z for 10~ 4 If the bonds between the is around 2 2 CO 3 carbon and oxygen are simple electron pairs the formal 1 and the expected value charge on the carbon would be 2 If there is one double bond of KI around 10~ (cf. Ill 7).
.
the formal charge would be zero and KI less than 10~~ 7 4 10~~ therefore indicates some The observed value of 2
.
double bond resonance. Because of the weakness of carbonic acid, solutions of the normal carbonates are alkaline from hydrolysis: CO 3 H 2O = OH", The concentration of OH- in 0.5M Na 2 CO 3 is about O.Q1M. Bicarbonate ion can either
HCOr +
hydrolyze,
HCOr + H O = H CO +
2
OH",
or
it
can ionize further,
HCO - =
3
COs
+ H+.
as
is
The former reaction proceeds farther than the latter, shown by the faintly alkaline character of bicarbonate
tions; the concentration of
solu-
OH~
in a molal solution is
286
REFERENCE
[Ch. XIII
about 2 X 10~ 6 However, the two reactions tend to assist each other, due to the neutralization of H+ and OH~; each goes farther than it would in the absence of the other,
.
giving as the result the summation in the reaction,
2HCO
The
is
H CO +
2
COs
1.1
equilibrium constant for this very important reaction X 10~4 corresponding to about 0.01 If CO 3 and
,
in Because of this equilibrium, 3 are readily converted to bicarbonate by passing carbonates carbon dioxide into their solutions or, if they are but slightly
2
3
.
;
O.OOf
H CO
M NaHCO
soluble, into a suspension in water. very important of such a conversion is the solution of calcium carexample
bonate in excess carbon dioxide:
CaCO + H CO 3 =
3
2
Ca"
2HCOs~. The equilibrium is displaced upon heating by the evolution of carbon dioxide, hence bicarbonates in solution form carbonates upon heating, upon evaporation, or upon neutralization of the carbonic acid. The first of these processes accounts for the formation of scale in kettles and
second for the formation of stalactites and staand the third is used in the softening of water by addition of alkaline reagents. The carbonic acidbicarbonate equilibrium is also important in maintaining the pH of the blood. With the exception of the alkali metals, most of the carbonates are but slightly soluble or else hydrolyze to form basic carbonates or hydroxides. The bicarbonates of the alkali metals are less soluble than the carbonates; those of other metals generally more soluble. Reference should be made to the alkali carbonates for the details of their comboilers; the
lagmites in caves;
mercial preparation. 11. Analysis of Carbonates. Carbonates are detected in qualitative analysis by the evolution of carbon dioxide with acids, and the formation of a white precipitate when this is passed into a solution of barium or calcium hydroxide.
12]
CARBON
287
When
more
only a trace of carbonate is present, the test is made by adding a small piece of zinc to the sample, so that the hydrogen evolved will carry the carbon dioxide through the lime water.
delicate
The indicator, methyl orange, changes from yellow to red at about 10~4 H+; hence, a dilute solution of carbonic acid gives a yellow color; but if a drop of strong acid is added, the color changes to red. Carbonates may, therefore, be titrated with a strong acid, using this indicator.
An
alternate
method
is
to
add an excess of standard acid, remove the carbonic acid by boiling, and titrate the excess
of acid with alkali, using phenolphthalein as an indicator.
10
-HCOy
10
In case hydroxide is present, the carbonate may first be
10
removed by precipitation as barium carbonate. In a mixture of soluble carbonate and

bicarbonate, the solution may first be titrated in the cold
10
with a strong acid, using phe10

10
cc,
20 30 ofO.IM HCI added
40
FIG. 3. Tit ration of carbonate with
nolphthalein as an indicator, which gives the amount of carbonate. To another portion
hydrochloric acid.
methyl orange
is
added, and
step
the titration
is
carried to this end-point.
The second
corresponds to the sum of the moles of bicarbonate and twice the moles of carbonate. Or, the analysis may be made (1) by addition of excess of standard base, (2) precipitation of the carbonate
by barium
the carbonate and determination
ion, (3) filtration of of total carbonate by ti-
tration, (4) titration of hydroxide in the filtrate to give the amount of bicarbonate by difference.
Peroxycarbonates. Salts of the type Na 2 CO4 and 2 C 2 O 6 are known, corresponding to the acids
12.
288
REFERENCE
[Ch. XIII
H
I
O
I
00
II
II
O=C O O H
and
H O C O
C O
H,
but the free acids are unstable. The monoperoxycarbonates are formed by the interaction of an alkali carbonate and hydrogen peroxide. They may be precipitated from
the solution
acid
The salts of may be prepared by the anodic
by
ether.
the diperoxycarbonic oxidation of solutions

10
or below.
of alkali carbonates, cooled to
These
compounds show the characteristic strong oxidizing power and strong reducing power of other peroxyacids and of hydrogen peroxide. The commercial sodium peroxycare.g.,
bonate often contains hydrogen peroxide of crystallization, Na 2 CO 4 'H 2O2. 13. Carbides. Carbon combines directly with many metals at high temperatures to yield carbides. All the main Group I metals form carbides of the general formula,
and the main Group II (except beryllium), 2C 2 2 These compounds and also Cu 2 C 2 and Ag 2 C 2 hydrolyze in water with the evolution of acetylene. The rare earth metals form carbides of the same general formula, 2 but these and other dicarbides, as UC 2 ThC 2 and MnC 2 hydrolyze to form complex mixtures of solid and liquid hydrocarbons. Beryllium carbide, Be 2 C, and aluminum carbide, A14 C 8 and a number of group four compounds, as SiC, hydrolyze to form methane and the carbides Fe 3 C, Mn 3 C, and Ni 3 C yield chiefly methane with some
;
MC
MC
hydrogen.
bides as
In addition to these so-called salt-like carbides,
there exists a
B 6 C, ZrC, HfC, TaC, Cr8 C 2 W 2 C, VC, Mo 2 C, and MoC. These carbides are high melting and very hard.
,
number
of comparatively non-reacting car-
The mixed
carbide
as a hard tool cutting edge*
WTiC known as Kennametal, is used No carbides are formed by

2,
16]
CARBON
of the first or the second subgroups, or antimony, or bismuth.
289
members
by
tin,
lead, arsenic,
Commercially, the most important carbide is calcium This is made by heating a mixture of lime and carbon in an electric furnace (about 3000) CaO + 3C = CaC 2 + CO. The reaction is highly endothermic. The formation of acetylene and cyaniamide from the carbide is discussed under those compounds. 14. Carbon and Sulfur. The disulfide, CS 2 is formed by heating carbon and sulfur in an electric furnace: 2S = CS 2 C It is also made commercially by the
carbide.
: ,
reaction of sulfur vapor and hydrocarbons,
e.g.,
CH +
4
4S
= CS 2
+ 2H
2 S.
The compound
is
a heavy, colorless, volatile, highly re-
fractive liquid. It usually has a disagreeable odor from the presence of other sulfur compounds. It has acid properties, and unites with basic sulfides forming thiocarbonate :
The liquid is a good solvent. The 3 inflammable and poisonous. It is used in vapor highly killing rodents, as a solvent for rubber and sulfur, in the preparation of carbon tetrachloride, and in the manufacture
2
.
BaS
+ CS = BaCS
is
of viscose.
prepared by the action of ozone upon carbon disulfide vapor. It may be condensed as a liquid at very low temperatures; upon heating, it polymerizes with explosive violence to a solid. 16. Carbon oxysulfide, COS, forms when carbon disulfide is treated with sulfur trioxide CS 2 + 3SOs = COS + 4SO2. It is a colorless gas, and resembles carbon dioxide in being
is
:
The monosulfide, CS,
rather soluble in water.
heavy hydrocarbon molecules has been discussed in the introductory paragraphs of this chapter. These compounds may be considered in two main groups.
(1)
16.
Carbon and Hydrogen,
The formation
of
eral
compounds. The paraffin series, genformula, Cn H (2n + 2) occurs extensively in American
The
aliphatic
290
REFERENCE
oils.

lighter
[Ch. XIII
mineral
The
C4Hio, constitute natural gas. CgHis, constitute the light and

bers,
members of the series, CH 4 to The compounds, C 6 Hi 2 to heavy gasolines. The memoils,
CH
9
2o
to Ci 3
28 ,
Various heavier molecules, up unsaturated derivatives of the paraffins (Par. 2) may be considered as separate series: such as compounds of the general type, C n H 2n the olefine series, and C n 2n _ 2 acety,
are familiar as lubricating to C 3 5H 7 2, as paraffin wax.
and
lene series.
(2) Aromatic compounds, consisting of benzene, C 6 He, and its simple derivatives, such as toluene, CH 3 C 6 H 5 and more complicated double and triple ring compounds, such as naphthalene, CioH 8 and anthracene, Ci 4 Hi
;
H
C
H HCH
C
H
CH
HC
HC
CH
HC
HC H
Toluene
H/V\H
HC
CH
CH
H
Benzene
Naphthalene
These hydrocarbons occur in certain types of mineral oils and in the liquid condensate from the destructive distillation of coal.
constituent of natural gas.
has been mentioned as the principal It was formerly known as marsh gas, and was first observed as bubbles rising from the decomposition of vegetable matter in swamps. The gas has a low freezing and boiling point, and is but slightly soluble in water (5.5 cc. per 100 cc. of water at 0). The gas may be formed by the direct reaction of carbon and hydrogen, at moderately high temperatures, Table VI.
17.
Methane,
CH
4,
18]
CARBON
TABLE
C + 2H 2 = CH +
4
291
VI
EQUILIBRIUM VALUES FOR THE REACTION,

17,889 cal.
The reaction is obviously favored by high pressure. Methane is also formed by the reaction of carbon monoxide and hydrogen:
CO + 3H = CH + H
2 4
O,
at
low
temperatures, 250-300, in the presence of certain catalysts (Par. 6). At high temperatures, the equilibrium is reversed.
The laboratory preparation of methane is usually carried out by heating a mixture of sodium acetate and soda lime, or by the action of water on aluminum carbide CH^COONa + NaOH = Na 2 CO 3 + CH 4 and A14 C 3 + 12H 2 O = 3CH 4
:
4A1(OH) 3
18. Acetylene, C 2 2 is formed in small amounts by the reaction of carbon and hydrogen at very high temperatures
,
(2500)
2C
+H =CH
2
2
2.
It is
prepared commercially
by
the action of water on calcium carbide:

2
CaC + 2H O
2
2
= C
H +
2
Ca(OH)
2.
and odorless when pure, but usually has a pungent odor due to the presence of traces of phosphine. The vapor pressure of the liquid is about 40 atmospheres at 20; and under these conditions it is highly
The gas
is colorless
explosive, as at ordinary temperatures the gas is unstable in respect to hydrogen and carbon. It is usually handled
as a solution in acetone under pressure in steel cylinders. The temperature of the oxy-acetylene torch, 2500 to 3000 C., is hotter than that of any other flame, with the
possible exception of that of atomic hydrogen (cf. I 9); and this is employed extensively in cutting and welding Before the introduction of the steel and other metals.
incandescent electric globe, the acetylene lamp was of considerable importance.
292
REFERENCE
[Ch. XIII
Acetylene acts as a very weak acid. Silver acetylide, Ag 2 C 2 is formed by passing the gas through a solution of silver ammonia hydroxide. Many of the acetylides are
,
explosive.
of
At high temperatures acetylene polymerizes to a number complex products, among them being benzene, 3C 2 H 2 SB CeHe. As an unsaturated compound, it readily adds
its
halogen derivatives of the type C 2 H 2 X4. The condensation of acetylene also yields derivatives Thus vinyl acetate, of the vinyl group, CH 2=CR~. is made by the condensation with CH 3 2 acetic acid, using mercuric oxide and sulfur trioxide as a catalyst. This and similar derivatives form the basis for the rapidly developing vinyl plastic industry. In the presence of mercurous sulfate acetylene adds water to form acetaldehyde, CH 3 CHO. This may be reduced to ethyl
hydrogen or halogens to form, respectively, ethane or
COOCH=CH
alcohol or oxidized to acetic acid.
Oxidation Products of the Hydrocarbons. The oxidation of methane leads to the following series of oxidation
19.
products
HO
C
i,
H H C O H H 0=0 H C O H O=C=O A
Methyl
alcohol
Methane
Formaldehyde
Formic
acid
Carbon
dioxide
The
half reactions involved in these oxidations
and
their
approximate potentials in water solutions are given below. The couples are not reversible at room temperature.
VOLTS M*
CH -f H 2O - CH,OH + 2H+ + ler CH OH - HCHO + 2H+ + 2e~ HCHO + H O - HCOOH + 2H+ + 2<r HCOOH - COa + 2H+ + 2er
4
_ -
0.58 0.24 0.01 0.14
Related compounds result from the oxidation of other hydrocarbons; and these compounds are generally classified
f21J
CARBON
293
>n the basis of the following characteristic groups,
where
epresents an organic radical formed by the removal of one lydrogen ion from a hydrocarbon, e.g. ethyl, C 2 6 from
;thane,
R.
OH
O
||
H
Alcohols
organic bases
|
Aldehydes
O
Ketones
*
3.
R
Ethers
cules
RC OH
by removing water from two
alcohol mole-
||
Acids
O R
O
||
Esters
"salts" of an alcohol
JC
OR
and organic
acid.
20. Carbohydrates. An important class of organic comDounds contains hydrogen and oxygen in the same propor:ion as in water, and are termed carbohydrates. The group
ncludes cellulose, (C 6 Hi O5)y, starch, (C 6 HioO 5 )*, and the The latter are generally classified as monosac;harides, C 6 Hi 2 O 6 such as glucose or fructose; and as lisaccharides, Ci 2 22 On, such as sucrose (cane sugar), or actose (milk sugar). These compounds are really alcohol, ind aldehyde or ketone derivatives of long chain hydrosugars.
,
:arbons,
e.g.,
glucose
is
CH OH-CHOH-CHOH-CHOH2
CHOH-CHO.
The molecular weights of cellulose and starch are not cnown, but the molecules are very complex. Starch may DC converted to glucose by boiling in a solution containing a
xH 2O = xC 6 Hi2 O 6 . hydrochloric acid: (C 6 Hi O 6 )* Under similar conditions, sucrose may be hydrolyzed to a nixture of glucose and fructose.
ittle
a lydrocarbon is capable of being replaced by a halogen atom, Jius making possible thousands of halogen hydrocarbon
21.
Halogens and Hydrocarbons.
Any hydrogen
in
294
REFERENCE
[Ch. XIII
derivatives.
The replacement can
often be accomplished
by
direct action of the halogen as a gas, or in alkaline soluC1 2 = C 2 5 C1 tion upon the hydrocarbon, e.g. C 2 6
H +
Reactions between alcohols and halogen acids + + HC1 = C 2 H 5 C1 + 2O, may also be employed: C 2 H 6 A few of the more important compounds are discussed below. Carbon tetrachloride, CC1 4 is made by passing a mixture of carbon disulfide vapor and chlorine through a red hot tube: CS 2 + 3C1 2 = CCU + S 2 C1 2 The tetrachloride may be separated by fractional distillation from the sulfur chloride. Or, the reaction may be carried out by passing chlorine gas through the disulfide in the presence of a small amount of iodine. Carbon tetrachloride is a heavy, colorless liquid. It is non-inflammable, and a good solvent for non-polar
HC1.
OH
substances; whence its use in dry cleaning, and in fire extinguishers, e.g. "pyrene." The vapors are slightly toxic. If partial hydrolysis to phosgene, COC1 2 occurs, the vapors are highly toxic.
,
Chloroform,
CHC1
3,
is
ing powder on alcohol. largely as an anaesthetic.
prepared by the action of bleachIt is a heavy liquid, and is used
prepared by the action of iodine in alkaline solution on alcohol. It is a solid with a pungent
lodoform,
3,
CHI
is
characteristic odor,
and
finds extensive use as
Ethyl chloride, with chlorine in the sunlight, or alcohol is treated with phosphorus pentachloride. It is a volatile liquid which is employed in refrigerant cycles, and as a local anaesthetic, Ethylene dichloride, C 2 4 C1 2 is used in the manufacture of the polysulfide rubbers such as Thiokol, through its reaction with polysulfide. The product, C 2 4 S 2 polymerizes in the presence of zinc oxide to a plastic. The dichlordi-
C 2H
6 C1, is
an antiseptic. formed when ethane is treated
fluormethane, CC1 2 F 2 called Freon, has become important a$ a non-inflammable readily condensable gas for refrigera,
tion cycles. Cf. also
CF, Par.
4.
23]
CARBON
295
Fluorocarbons are synthesized from the corresponding hydrocarbon by direct reaction with fluorine or more readily by the action of such oxidizing fluorides as cobaltic
fluoride,
CHi + 28CoF
4
=*
CF
6
14
14HF
28CoF
These compounds are remarkably inert and are becoming important in the manufacture of chemically resistant plastics, high temperature lubricating oils and high temperature solvents.
Carbon and Nitrogen. The nitride, C 2 N 2 cyanogen, be considered as the polymerized free cyanide radical, may since it is formed by the oxidation of cyanides. The chemistry of the cyanides resembles in many respects that of the halogens, especially iodine; and the methods of preparation of cyanogen, by heating the compounds of the noble metals, and by the reaction with cupric ion, are analogous to the
22.
,
under these conditions: 2AuCN = 2Au = Hg + C N 2Cu++ + 4CN~ = 2Cu+ C N Hg(CN) CN + C N The reaction, C N = 2C + N 8 is highly exothermic (about 80,000 cal.). Many references are made
liberation of iodine
2
2,
2,
2.
chemical literature to the formation of cyanogen in it is doubtful if, even at that high teman appreciable quantity of the compound can be perature, formed by direct union of the elements. Cyanogen is a colorless gas, has a distinctive odor, and is extremely poisonous. It is soluble in water (4 volumes per 1 volume of water at 0). When heated to 400 the gas to a white solid, paracyanogen, (CN) X In polymerizes
in the
the electric arc, but
cyanogen hydrolyzes to cyanide and cyanate: C 2 N 2 + 2OH~ = CN"" + CNCT + H 2 O (compare C1 2 + 2OH~ = Cl~ + CIO- + H 2 O), In sunlight, it decomposes, forming ammonium oxalate, ammonium formate, and urea. The potentials for the oxidation and reduction of
alkaline
solution,
C N2
2
c23.
H O + fC N = HCNO + H+ 0.27 volt and HCN = iC N + H+ + e~, - 0.33 volt.

in acid solution are:
2 2 2
2
Hydrogen Cyanide, or "prussic acid," may be prepared by the action of dilute sulfuric acid upon an alkaline
296
REFERENCE
it is
[Ch.
XIH
cyanide, as
sulfuric acid,
a weak volatile acid. With concentrated carbon monoxide is evolved: H 2O
H+ = CO +
NH +.
4
HCN +
The
acid
is
also liberated
by the
dehydrating action of phosphorus pentoxide upon ammonium formate: HCOONH 4 = + 2H 2 O. Compounds of hydrogen cyanide with sugars (glucosides) occur in nature, e.g. in leaves and seeds of the peach tree; a solution made by boiling peach leaves in water was used by the ancient Egyptians as a poison. A recently developed process for the manufacture of 3 as the raw matehydrogen cyanide employs CO and Methanol is reacted with carbon monoxide at high rials. This product is then pressure to form methyl formate. with ammonia to give formamide and methanol, treated which is thus regenerated: CH 3 OH CO = CH 3 OOCH
HCN
NH
and CH 3 OOCH + NH 3 = HCONH 2 + CH 3 OH. The formamide is then dehydrated at 200 C. over alumina
2 2 O. Liquid hydrogen cyanide boils at 26.5. The gas has the odor of bitter almonds, and is extremely poisonous. Death results in a few minutes from breathing concentrations as low as 2 mg. per liter. It is readily soluble in water, like the halogen acids; but, unlike them, it is a weak acid, 10 With chlorine in solution cyanogen Xis = 4 X 10~ C1 2 = HC1 chloride is formed: CNC1. This
.
HCONH
HCN + H
HCN +
and
is
substance
"
gases.
is
also toxic
one of the well known "war
oxidizing agents oxidize cyanide to cyanate (see below), while acid oxidizing agents usually yield carbon dioxide and ammonia. The liquid is unstable
Alkaline
decomposition into the elements, and occasionally explodes. It is also difficult to keep because of the formation of solid polymers. The arrangement of the 10 electrons in cyanide ion may
with respect to
its
be
or
or probably both with resonance
between the structures.
When
the bond between the car-
25]
CARBON
297
bon and nitrogen

thus,
is broken by hydrolysis, however, 8 of the 10 electrons go with the nitrogen, forming ammonium:
HCN +
2H 2O =
+ 4H O
2
HCOONH COONH
4,
(ammonium
oxalate.
formate), and
CN
2
COONH
(cf.
ammonium
4
24.
The
Alkali Cyanides are important commercial com-
pounds
IV
21).
They may be prepared:

fusion with
(1)
4
from
6
alkali ferrocyanide
by
sodium metal
K Fe(CN)
+ K CO
2
2Na = 4KCN
+ 2NaCN +
carbonate:
2
2
Fe;
ferrocyanide
with
(2) by Fe(CN) 6
heating
the
3
= 5KCN
3
+ KOCN + CO +
Fe;
(3)
2
by the
;
reactions:
(300-400 C.) and 2 2 heat) (4) from calcium cyanamide by fusion with sodium carbonate: CaCN 2
2NH + 2Na = 2NH Na + H 2NaNH + 2C = 2H + 2NaCN (red
+ C + Na CO = CaCO + 2NaCN;
2
3
(S)
by the Biicher
of
process for the fixation of nitrogen,
by heating a mixture
sodium carbonate, carbon, and iron (catalyst) made into bricks in an atmosphere of nitrogen: Na 2 COs + 4C + N 2 = 2NaCN + 3CO. The cyanide is extracted with liquid ammonia. The alkali cyanides are readily soluble in water, and the
solutions are alkaline
are formed
by hydrolysis. Many complex cy~ anides are remarkably stable. Ions of the type (CN) 4 4+n
Ag(CN) 2
26.
by Cu+, Cd++, Ni++, Hg++, Pd++, and Pt++; of the type M(CN) 6 6+n by Cr++, Cr^+ Co++ Co+++, Fe++ Mn+, Mn++, MU+++, Rh+++, Ru++, Os^, Ir+++, and V+4 A few complex cyanides of the type ~" " M(CN) 3 3 hn are known, e.g., Cu+ Ni+ Mn"^", but they usually readily add another group. Silver forms the ion ~4 4
,
W+
forms
W(CN) 8
Cyanates are readily prepared

:
by the
action of mild
oxidizing agents
by heating upon + PbO = KOCN potassium cyanide with lead oxide Fb. The salt is extracted from the lead with alcohol, as
cyanides, for example,
KCN
298
REFERENCE

is
is
[Ch. XIII
the water solution
unstable:
also
:
KOCN + 2H O = NH
2
~
formed by the action of cyanide Cyanate ammonia ion 2Cu(NH 3 ) 4 H + 3CN~ + 2OH~~ upon copper
3.
~
+ KHCO
- 2CuCN + OCN- + 8NH 3

nate potential
+H
2
O.
The cyanide-cya2<r
is
CN- + 20H- = OCN- + H

The
0.97 volt
free acid decomposes very readily into carbon dioxide and ammonia in water solution. Ammonium cyanate,
NH
OCN,
is
isomeric with urea:
NH OCN
4
= CO(NH
2 ) 2.
The rearrangement takes

ous solution.
place upon evaporating an aque-
26. Thiocyanates may be prepared by fusing alkali cyS = KSCN. The ammonium anides with sulfur: salt is formed by the reaction of ammonia and carbon disul-
KCN +
4
fide:
4NH + CS = NH SCN + (NH

3
4 ) 2 S.
.
At 140,
this
salt
The free acid, rearranges to thiourea, CS(NH 2 ) 2 is a liquid which readily polymerizes to a yellow HSCN,
solid.
Calcium Cyanamide is important in its relation to the cyanamide process for the fixation of nitrogen. Around 1000, calcium carbide absorbs nitrogen to form cyanamide:
27.
CaC 2
+ N = CaCN +
2 2
3
.
as a fertilizer, the nitrogen
used directly or treated with superheated steam to convert

C.
is
The product
+ 2NH
is
into ammonia: CaCN 2 + 3H 2 O = CaCO 3 At low temperatures, the hydrolysis product
cyanogenamide:
2 ) 2.
2CaCN
+ 4H O =
2
2Ca(OH) 2
world's production of cyanamide in 1938 was about a million tons, but has decreased in recent
years.
28.
+ (CNNH
The
The Proteins
nitrogen
constitute a class of extremely

in
com-
plicated
animal and vegetable tissue. Empirical formulas, calculated from the percentage composition, give results such as Ci 46 H 226 N 44 SO5 but the molecular weights appear to be much higher. The
compounds, occurring
proteins are complexes of amino-acids,
i.e.
compounds con-
29]
CARBON
I
299
taining the groups
NH C
2
and
COOH,
such as glycine,
CH NH COOH.
2
2
THE ORGANIC CHEMICAL
INDUSTRIES
to the use of inorganic chemicals in various organic industries. For the sake of clarifying these references, brief outlines of some of the more important industries will be given.
29. Explosives.
is
Many
references have been
made
One
by
2.
of the
most important explosives

This compound
3
nitroglycerine
(cf.
also XII
36).
is
easily
detonated
2
shock:
4C
H (NO
5
)3
very
12CO 2
Like all good explosives, the heat and the gaseous products tend to large, occupy a very large volume in comparison to the original compound. Dynamite was formerly made by absorbing nitroglycerine in a porous earth this form is now generally
of the reaction
is
;
10H 2 O
+ 6N + O
replaced by solutions of guncotton in nitroglycerine, known as blasting gelatine, giant powder, etc. Diethylglycol
dinitrate,
C H (NO
2
4
3) 2,
is
now being used somewhat

or
cellulose
in
in place
of
6
nitroglycerine.
7
C H O2(NO 3 )3,
is
Guncotton, formed by steeping cotton
trinitrate,
a cold mix-
It explodes when detonated another explosive. Smokeless powder, or cordite, is by made by evaporating a solution, in acetone, of guncotton, nitroglycerine, and a little vaseline.
ture of nitric and sulfuric acids.
explosives employed in shells to produce violent are trinitrotoluene, "TNT," 2 (NO 2 ) 3 3C6 shattering a mixture of ammonium nitrate with TNT, known as
The high
CH
amatol, picric acid,
C 6 H 2 (OH) (NO
2) 3
and
RDX or cyclonite,
CaNeOeHe. The development and production of the latter was an important factor in World War II. These high explosives can stand the shock of being fired from a gun and require detonators which set up high shock waves such as
lead azide to cause
them
to explode.
TNT
is
not readily
300
REFERENCE
[Ch. XIII
exploded by the ordinary detonators and an explosive of intermediate sensitivity or "booster" such as tetryl is employed in addition to the detonator.
CH
O N N CH
2
ON C
2
C NO 2
:
ON C
2
C NO C H
H-
Y
NO
H C
Y
NO
TNT
Tetryl
NO
HC
2
\CH
ON N
2
Y
H
2
N NO
RDX
The extraction of pure cellulose from the 30. Cellulose. mineral and ligneous matter of wood and other plant fibers (especially cotton) has become one of the most important chemical industries. The wood or plant fibers are ground with water to give a mechanical pulp. Three types of chemical pulp, consisting of more or less pure cellulose are in use in America: (1) soda pulp, made by heating the mechanical pulp with 10 per cent NaOH under pressure, (2) sulfite pulp, made by digestion with a solution of calcium bisulfite
and free sulfurous acid, (3) sulfate pulp made by treatment with sodium sulfate solution which contains some NaOH and Na2S. Large quantities of chlorine are also employed
31J
CARBON,
301
straw are treated by the Pomelio process which employs chlorine gas in dilute sodium hydroxide to dissolve out the non-cellulose constituents. There are three forms of celluis insoluble in 18 per the most desirable. Cotton linters give a pulp which is 98 per cent alpha cellulose. Paper is made from various mixtures of mechanical and chemical pulp, the proportion depending upon the type and
lose, a,
j3,
and
7.
The alpha form

is
cent
NaOH
at 20 C. and
grades.
For the synthetic

lose is dissolved
textile
and
plastic industries the cellu-
cellulose is
by one of the following methods: (1) the treated with CS% and NaOH to form a xanthate
solution (viscose process).
The
cellulose
is
reprecipitated
(2) The cellulose is nitrated and the nitrocellulose dissolved in suitable solvents. (3) The solvent is ammonia-
by
acid.
cal
bath.
The cellulose is coagulated in a caustic Cellulose acetate is made by dissolving the pulp (4) in a mixture of acetic anhydride and glacial acetic acid.
copper solution.
Cellulose acetate may be precipitated by water. The process modified to give other esters in addition to the acetate
also cellulose ethers.
31.
is
and
Rayon and other Textiles.
Any
of the cellulose solu-
tions discussed above may be employed to form threads. The liquid is forced through a small opening and coagulated.
The
resulting thread is gathered, washed, and wound. The 1950 production of American rayon was about a billion pounds. About 70 per cent of this was produced by the
viscose process
although this
nylon is nearly like natural

2
2)6 2
and practically none from nitrocellulose was the first of the artificial silks. The new not a cellulose but is a polymide and thus more
silk in
2
composition.
2) 4
H N(CH NH + NH OC(CH CONH2

Hexamethylene
diamine
-
Adipamide
r
|_
o
C
OH
(CH a ) 4C
N (CH,)
H N
I
_L
Nylon
302
REFERENCE

of the earliest plastics
[Ch. XIII
32. Plastics.
One
was
celluloid
which was made by combining nitrocellulose with camphor and castor oil. Dissolved in alcohol and ether, the nitrocellulose formed a lacquer known as collodion. The name Pyroxylin is now given to this class of plastics and lacquers. The plasticizing agent camphor has now been supplemented by many others such as the organic phosphates, and derivatives of phthalic acid. This is an example of a Such materials become soft and pliable thermoplastic.
thermoplastics polymerize bonds. The poly vinyl, polystyrene, polyacrylic esters, and cellulose acetate are examples.
when
heated.
In
general,
through
carbon-carbon double
CH
ri2C=C
3
"
H CH
C C
"
c=o
O CH
. 3
H CH
3.
Methyl methacrylate
Lucite, Plexiglass
O
II
H H
I
I
CH C-OC=CH
3
H H
C C
1
A
A
0=C CH 3jn
Vinylite
Vinylacetate
A new type of plastics made from tetrafluoroethylene and other fluorohydrocarbons has recently been introduced. Teflon is an example. These are very resistant to acids and
even at high temperature. resins do not soften readily when heated and are hard and tough. Their structure indicates that they have many more cross-linkages than do the
alkalies
The thermosetting
thermoplastics.
33J
CARBON
303
The phenol-formaldehyde resins such as Bakelite were among the earliest of this type. Other examples are:
plaskon from urea and formaldehyde, glyptal from poly-
hydroxy alcohols, and polycarboxylic acids and melmac from melamine and formaldehyde. 33. Rubber. Natural rubber is a type of thermoplastic
CH
I
made up
raw rubber as it conies from the plantation is a soft sticky substance. At the factory it is softened with steam and mixed with compounding agents (principally carbon black and zinc oxide) and with the
together in
vulcanizer,
sulfur.
of isoprene units, long chains. The
CH C=CH CH
2
linked
temperature of 120 to
Vulcanization requires heating to a 200 and results in cross linkage
between the long carbon chains.
CH
H H
C
H
I
CH
H H
! I
-C -C=C
C C C C
I I
I
"1 i"
H H
I
-C C C C
H
CH
3
H H
H
CH,
Unvulcanized chains
Vulcanized chains
304
REFERENCE
[Ch, XIII
Vulcanization decreases the plasticity and increases the Small objects are often vulcanized the vapor cure, using sulfur chloride. Recent developby ments have been the introduction of "accelerators" such as
resistance to abrasion.
hexamethylenetetraamine, (CH 2 )eN4, which lower the temperature and the time required for vulcanization and of
"anti-oxidants" which retard the appearance of brittleness due to atmospheric oxidation.
The
following are the

(1)
thetic rubbers:
and styrene, butadiene and vinylcyanide,

4
6,
CH
more common types of the synbuna S, a co-polymer of butadiene, C2H 3 C 6 H5; (2) buna N, polymer of
mer
of chloroprene,
butylene C 4 8 and hydrocarbons; (5) thiokal,
(3) neoprene, polybutyl, polymer of isosmall amounts of other unsaturated

2
3
C H CN;
(4)
CH
4
C1;
made from
ethylene dichloride
and sodium tetrasulfide. In 1945 over 800,000 tons of GR-S, buna S type rubber, were produced, largely for the manufacture of automobile tires. In this process butadiene and styrene are emulsified and the temperature of the emulsion raised to bring about polymerization. Various catalysts have been developed to effect the polymerization at low temperatures (cold rubber).
H H H H
H H
H H H H H H
I
'
c :=c c c c
H
Butadiene
Styrene
is
H H
Buna S Rubber
Although the buna-S
by
far the
most important type
of synthetic rubber, fairly large quantities of neoprene are produced for the manufacture of innertubes. The thiokals are used as material resistant to solvents and to abrasives.
varies greatly in composition. Some oils (the Pennsylvania) contain largely members of the paraffin series, while others (the California) consist of
34.
oil
Petroleum.
Crude
34]
CARBON
305
aromatic groups with varieties of side chains. The properand heavy constituents also vary from one field to another. By distillation the crude oil is separated into (a) volatile gases, (b) gasoline, (c) solvent naphtha,
ties of light
(d) kerosene, (e) lubricating
oil,
(f)
wax
tar
and
fuel oil.
The
various products are agitated with sulfuric acid, and washed with water and dilute caustic soda. If the crude is high in sulfur an agitation with a solution of lead oxide in sodium hydroxide may also be used. Since the greatest
demand has been
for gasoline, the higher-boiling conare heated to a high temperature (' 'cracking") stituents to cause their decomposition into lighter hydrocarbons.
However, the older methods are being displaced by more One of these is the catalytic hydrogenation of both the heavy fractions and also of the gas oil. This tends to remove oxygen, nitrogen, and sulfur as their hydrogen compounds, to remove the unsaturated molecules which tend to condense to form gumând to give superior lubricating oils and gasolines. Another recent development has been the polymerization of the more volatile constituThe hydrocarbons ents, especially propane and butane. are generally cracked at relatively low temperature, cooled, and catalytically polymerized. The solvent extraction method by which a lubricating oil may be resolved into a desirable paraffinic oil and a less desirable, less heat resistefficient processes.
ant fraction by the use of selective solvents such as phenol
and dichloroethyl ethers is now in general use. Modern refining methods endeavor to promote the formation of branch chain hydrocarbons, such as isooctane, which have
high "anti-knock" qualities. The use of lead tetraethyl, Pb(C2H 5 ) 4 as an "anti-knock" has also become universal. During World War II the German chemical industry made a major portion of the gasoline required for their
,
and carbon monoxide by the Fischer-Tropsch process. With various catalysts the process yields products ranging from methyl alcohol to long
military needs from hydrogen
306
REFERENCE
[Ch.
XW
This process makes available fuel oil from coal to supplement our oil reserves. The direct hydrogenation of coal at high pressures is an alternate process which may prove more efficient than the FischerTropsch process. The American petroleum industry now produces annually some 2 million tons of chemicals. These include such substances as butadiene and styrene for rubber, toluene for TNT and the dye industry, glycerine and ethyl alcohol. In 1949 about 70 per cent of the total production The ethylene is of ethyl alcohol was from ethylene.
chain hydrocarbons.
hydrated,
lytic
C H4
2
+ H O = C H OH,
2
2
either
by
direct cata-
hydration or by the hydrolysis of ethyl sulfate, formed by absorbing ethylene in sulfuric acid. 35. Dyes, Pharmaceuticals and Vitamins. The remarkable development of synthetic organic chemistry proceeds at an accelerated pace. In 1828 Frederick Wohler amazed the scientific world by the production of urea from ammonium cyanate. Previous to that time, it was generally believed that organic compounds could only be synthesized by living organisms. In 1930 urea sold for 80 cents a pound. In 1949 it was produced for less than 4 cents a pound by In 1856 W. H. Perkins direct combination of C0 2 and 3 Now the synthetic synthesized the first dye (mauve). dye industry manufactures dye worth 200 million dollars
NH
annually. During World War II the Germans converted coal to acetylene, combined this with formaldehyde (also made from coal) to get propargyl alcohol, then allyl
This they combined with alcohol and finally glycerol. acids from the Fischer-Tropsch process (cf. Par. 34) fatty to get edible fats. Each year sees the synthesis and commercial production of many new organic compounds, duplicating or improving natural products. The production of vitamins, sulfa drugs and antibiotics has been a major achievement. Examples of the structural formulas of various types of complex molecules are given below.
35]
CARBON
'
307
CH OH
2
|CH 2OH
H HC O H
H H H H O O C C C=C C=O O H
O
Vitamin
CH
II
CH
C CH=CH C=CH CH=CH C=CH CH 2OH C CH3
\/ H
2
Vitamin
H H
C
I
HN C
2
CH
CH
H C
HC
V
H H
C
C C OC 2 H 4 N C 2 H 6
HC
V
I
C H
CH,
CH
Novocaine
C NH
Benzedrine
NH
i
H C H C
CO H
2
H C
C H
V
H
CH
H C
C H
S0 2 N
H
Aspirin
Sulfathiazole
308
REFERENCE
[Ch. XIII
H
C
H O H H H
CH
H
H
=C N
C COOH
Penicillin
G
C2H5
H
C
CC1 8
H H
C=C
C C
C' C
H C
Cl
C C
C H
Cl
O=C
H N
ii
V
H
|| H H
(DDT)
C=O N H
O
Dichlorodiphenyltrichloroethane
Veronal barbital
H N
H
C C H CO H
4 8 2
O=C
H
Biotin,
H
6 6
Vitamin B Complex
CeH 6
C C9H N(CH
4
3) 2
C H NH 2
CH
6
C H 4OH
6
C H N(CH
4
)2C1
CO
N
C H (NH
6
3
O
2) 2
C6 H OH
4
Malachite green
Bismarck brown
Phenolphthalein
Chapter
XIV
SILICON
second element of Group IV, occupies as a position in the mineral world as carbon does in important the vegetable and animal. Its chemistry is characterized by the stability and complexity of the compounds of the dioxide, SiC>2, with basic oxides. In this respect, it resembles boron more closely than it does carbon. Although it forms hydrogen compounds similar to those of carbon, the bond
1.
Silicon, the
between the silicons is readily broken, and the compounds do not possess the stability or importance of the corresponding carbon compounds. The oxide like that of boron is high melting and non-volatile, and many of its compounds are derivatives of polyacids, which resemble the boric acids. However, the majority of the silicates are salts of ortho or meta silicic acid, and thus contain the groups SiC>4 and SiOa, the former having a charge of + 4 and the latter of + 2. Although a monoxide is known, few + 2 or unsaturated compounds have been prepared. In connection with the resemblance between boron and
should be made (cf. Ill 7) to the similar" in the values for the field of force about B+3 and Si" 4 ity 2* Occurrence, Silicon is never found as the free elesilicon, reference
1
ment.
dioxide and its compounds constitute about 87 per cent of the earth's crust, and the element is estimated as forming 25.8 per cent of the outer portions of the earth.
The
Silicon thus ranks next to
cipal silicon minerals are
oxygen in abundance. The prinsummarized in Table VI, and the

309
310
REFERENCE
[Ch.
XIV
important groups, such as the feldspars, pyroxenes, amphiboles, and micas, are discussed in subsequent paragraphs. 3 Elementary Silicon has been prepared in a semi-metallic crystalline form, and also in a so-called amorphous form. The former possesses a grey luster and fair electrical conductivity (Table I). Both forms appear, from X-ray data, to have the same atomic arrangement in the crystal, the modified diamond type, hence the amorphous form is probably a mass of very small crystals.
Amorphous
silicon is
prepared by the high temperature
reduction of silicon halides ide by magnesium SiCl 4 +

:
by
4Na =
alkali metals, or of the dioxSi 4NaCl. the
When
sodium silicoNa2SiF 6 is reduced with excess of aluminum,

dioxide, or
fluoride,
,
the silicon dissolves in the

excess
cooling,
metal,
and
in
upon
the form.
separates crystalline metallic
This may be separated from

the
aluminum by
dissolv100
Per cent
SI
ing the latter in acid. The metallic form may also be

FIG.
1.
diagram. prepared by the reduction of the dioxide with carbon in an electric furnace, although it is difficult to avoid the formation of the carbide. Amorphous silicon may be converted to the metallic form by recrystallizing from molten silver.
Aluminum-silicon
TABLE
ATOMIC AND PHYSICAL PROPERTIES OF SILICON
5]
SILICON
is
311
Silicon
It is generally prepared,
of considerable importance in the steel industry. however, as ferrosilicon (Par. 6). Silicon burns in oxygen, 4. Reactions of the Element.
but not readily, as a surface layer of oxide tends to stop the reaction. It ignites spontaneously in fluorine at room temperature, in chlorine at 300-350, in bromine at 500; and the amorphous form reacts with iodine at red heat, but without luminosity. The oxidation reduction potential,
Si
is
+ 2H O =
2
SiO 2
+ 4H+ + 4e~: 0.6 volt,
not of great significance because of the slowness of the reThus, silicon is not soluble in hydrogen ion, but due to the great stability of silicates, it does dissolve in sodium hydroxide with the evolution of hydrogen. The element is also oxidized by steam. A mixture of nitric and hydrofluoric acid gives silicon tetrafluoride. Combination occurs with nitrogen and sulfur at high temperature, and with many metals to form silicides.
action.
TABLE
Si Si 4Si -f
II
REACTIONS OF SILCON
2X 2 = SiX 4 2NaOH + H O = Na 2 SiO SiO 2 4 2H 2 Si + 2H 2 O 3Si 4- 4HNO 8 4 12HF = 3SiF 4 Si 4- K 2 CO 8 = K SiO 3 4 C 3Si 4- 2N 2 - Si N Si -4 2S - SiS 2 nSi + mM = Si n M m
2 2 3
4
4O 2
SiO 2
'
Not rapid With halogens

With steam
+ 2H
4 4NO + 8H O
2
Fused
With many metals
many molten metals, and the temperature-composition curves indicate the formation of both solid solutions and definite compounds. Com3 Si, are formed by Li and Cu; of the pounds of the type, 2 Si, by Mg, Mn, Fe, Co, Ni, and Pd; of the type, type, MSi, by Mn, Fe, Co, Ni, Pt, and Pd; of the type, MSi2, by Ca, Co, Sr, V, and U; and of the type, MSi 3 by Co. A few of the more important compounds are discussed below.
6.
Silicides.
Silicon dissolves in
312
REFERENCE
[Ch.
XIV
Ferrosilicon. FeSi is made by reducing siliceous iron ore in an electric furnace. It is employed extensively in the
6.
steel industry, especially in the manufacture of silicon steels, the more important of these being (1) acid resistant steel, e.g. "duriron" (16 per cent silicon) and (2) steel of high
magnetic permeability. The

addition of silicon to iron
also reduces the
1600
FeSl
amount
of
1400
iron carbide, Fe 3 C; and thus | converts white cast iron into 1 grey cast iron. Silicon added |
1443
1425
to molten steel also serves as a "deoxidizing" agent.
130
C
\
1245
123E 20 40
Hydrogenite, a mixture of
ferrosilicon
1200
60
Si
80
100
and
solid
sodium
Per cent
FIG.
2.
hydroxide, evolves hydrogen upon the addition of water, and has been used as a source of hydrogen for balloons and air ships. 7. Silicon Carbide, SiC, is one of the hardest substances known. Although the data are somewhat indefinite, the
in the crystal appears to be a modified diamond .type of structure. It is manufactured extensively for use as an abrasive, by heating a core of
Iron-silicon diagram.
arrangement of the atoms
carbon packed in sand in an electric furnace: SiO 2 + 3C = CSi + 2CO. The furnace is of the resistance type, the carbon core serving as the heating element. 8. Calcium Silicide, CaSi 2 is formed by heating lime, sand, and carbon in an electric furnace CaO + 2SiO 2 + 5C = CaSi 2 + SCO. It is a powerful reducing agent, and is employed as a "deoxidizing" agent in steel manufacture,
,
and
also as a reducing agent in certain explosives. 9. Silicon and Hydrogen. The first 7 or 8 members of the series, Si n 2n+ 2 corresponding to the paraffin series, are
known. These hydrogen compounds resemble the hydrocarbons in physical properties, but not in stability. They
inflame spontaneously in air at
room temperature, or
11]
SILICON
313
slightly above, and are decomposed by alkali with the formation of a silicate and hydrogen. mixture of the various members of the series results from the action of acids upon
while lithium silicide, Li 3 Si, gives largely silicoe thane, Si 2 6 The existence of unsaturated hydrogen compounds is doubtful, with the exception
magnesium
silicide,
Mg
.
2 Si,
of the
compound SiH 2
10. Silicon
and the Halogens.
rectly with silicon, forming tetrahalides.
The halogens react diThe energy of the
with
reaction decreases with the increasing size of the halogens; fluorine, the reaction is spontaneous at room temperature, while
with iodine the reaction occurs only at red heat.
The
tetrahalides hydrolyze in water to form silicic acid and the hydrogen halide, and this hydrolysis is complete with all the tetrahalides, except the tetrafluoride. Due to
the stability of the fluoride, silicon dioxide and most of the mineral silicates dissolve in hydrogen fluoride: SiO 2 + 4HF = SiF4 2H 2 O. The solid tetrafluoride sublimes without
melting but under a pressure of 2 atmospheres it melts at 77. At room temperature the tetrafluoride is a gas with a pungent odor. With water, partial hydrolysis results in the formation of fluosilicic acid: 3SiF4 + 3H 2 O - 2H 2 SiF 6 + 2 SiO 3 This is a moderately strong acid, and its potassium salt is but slightly soluble. X-ray data on the solid fluosilicates show that the six fluorine atoms are arranged symmetrically at equal distances about the silicon atom. In the acid nature of the fluoride, silicon again resembles boron. 11. Silicon tetrachloride is prepared by the action of chlorine on silicon carbide, or on a hot mixture of silica and carbon: 2C1 2 + SiC = SiCl 4 + C; SiO 2 + 2C + 2C1 2
;
also
2CO. The product prepared by these reactions contains higher members of the series, Si n Cl 2n+2. Mixtures of the tetrachloride and ammonia have been emSiCl 4
ployed for the preparation of military smoke screens, since

in moist air solid silicic acid
and ammonium chloride are
314
REFERENCE
[Ch.
XIV
formed. With sulfur trioxide, the oxychloride, Si 2 also silicon dioxide results: 2SiCl 4 + 2SO 3 = + S 2 O 6 C1 2 and SiCl4 + 3SO 3 = SiO 2 + 2S 2 O 6 C1 2
, .
OQ
6,
and
fl
Si 2 OCl
12.
By
silicon,
chlorine hydrosilicons are formed, the

.
the action of hydrogen chloride upon heated most im-
This and other portant being silicochloroform, SiHCl 3 silicon hydrogen halides hydrolyze in water with the formation of oxyhydrogen compounds: 2SiH 3 Cl + 2O = 2HC1 + 2(SiH 3 ) 2O (Disiloxan): SiH 2 Cl 2 + 2O - 2HC1 + (SiH 2 )O (Prosiloxan): Si 2 Cl 6 + 4H 2 O = 6HC1
H H
+ (SiO H) (Silico-oxalic acid); 2SiHCl + 3H O = + H Si O (Silico-formic acid anhydride).

2
6HC1
SILICON AND
13. Silicon
OXYGEN
Monoxide.
SiO, may be prepared by excess silicon dioxide at temperatures .around 2000. SiO 2 C = SiO CO. The oxide is a solid at these tempera-
yellowish brown monoxide, the reaction between carbon and
The
tures, and unless rapidly cooled, decomposes: 2SiO = Si + SiO 2 It is used commercially under the name monox, as a pigment, and also as an abrasive. 14. Silicon Dioxide. Free silica, SiO 2 constitutes about 12 per cent of the earth's crust and this, together with silica
.
,
in combination with basic oxides, approximately 60 per cent. It occurs in three crystalline forms, quartz, tridymite,
and
cristobalite,
and each of these has a number
of modifi-
cations (Table III). It also exists as the supercooled liquid, or quartz glass. Sand, flint, and agate are familiar forms of silica. Kieselguhr, or diatomaceous earth, is silica resulting from the skeletons of diatoms. Quartz belongs to the hexagonal system with threefold
symmetry about its principal axis. The crystal has no plane or center of symmetry; and therefore exists in two forms called "right-handed" and "left-handed," which are mirror images of each other and rotate the plane of polarized
light in opposite directions (Fig. 3).
Crystals of enormous
14]
SILICON
315
found in nature. Quartz has a density of 2.65, and is somewhat harder than ordinary glass. It is very transparent over a range of wave-lengths extending from the infrared far into the ultraviolet (transmission for 1 mm. thickness = 67
size are occasionally
per cent
at
0.19
/i),
and
therefore finds considerable
application in the manufacture of optical instruments
and
As
a FIG.
3.
quartz at ordinary temperaslow at low temperatures, however, and both forms are found in nature, especially in lavas
tures.
Quartz crystals; a, righthanded; b, left-handed.
^
is
ultraviolet lamps. indicated Li Table III,
tridymite and cristobalite are unstable with respect to
The
transition
which have cooled quickly.
TABLE
III
MODIFICATIONS OF SILICA
highly viscous, and like all such liquids, readily supercools. Quartz glass has a lower density (2.2) than the crystals, and a very small coefficient of expansion,
Liquid
silica is
0.0 6 54 (linear). Because of its low expansion, it is possible to plunge white hot quartz glass into water without having
it
crack. Quartz glass does not soften below 1500, whereas
316
REFERENCE
[Ch.
XIV
ordinary glass softens around 600 to 900. Both of these qualities make it very valuable in the construction of appaIt should be ratus for high temperature measurements. noted, however, that helium and hydrogen diffuse rather
readily through quartz glass at temperatures as low as
300.
a
Quartz glass high temperature furnace.
is
now manufactured by
fusing pure
silica in
crystal structure of the three forms of silica may be represented as tetrahedral groups of oxygen atoms about a
The
central silicon atom.
The
at
tetrahedra
are
linked
each corner so that each oxygen is attached to two

silicons.
The high temperor

/3-modifications
ature
have a more definite structure and higher symmetry than the a-forms. /3-tridymite is similar to the wurtzite Structure and /3-CrystObalite
FIG. 4. Projection of silicon

in 0-quartz.
atoms
to
the
i.e.,
sphalerite
structure,
the silicon atoms are arranged like the carbon atoms of diamond. In /3-quartz the tetrahedra are more
closely packed.
In the unit cell the silicons are located in
three planes at different heights and the projection of the centers onto a single plane gives a hexagonal pattern,
Fig. 4.
The various forms of silica are soluble in alkalies with the formation of silicates, but they are only slightly affected by acids, except hydrofluoric which converts silica into the
tetrafluoride.
The great stability of silicon dioxide is re= SiO 2 lated to its high heat of formation Si 200 2 It is exceeded by that of the fluoride, however: Si kcal.
:
+O
+ 2F =
2
SiF4
+ 360 kcal.
The
is
15. Silicic Acids.
result of the addition of
acid to a soluble silicate
a strong the formation of a colloidal solu-
16]
SILICON
317
tion,
Upon
or hydrogel, of the general formula, mSiO 2 -nH 2 O. heating, the gel may be gradually dehydrated and the
dioxide formed.
Partially dehydrated gels have high absorbent power, and are now used commercially in the absorption of benzene, sulfur dioxide, nitric acid, nitrogen dioxide, and other vapors. Many forms of hydrous silica occur in nature, such as opal and agate.
and mineral derivatives of a large number of silicic acids are known. The nomenclature of these hypothetical acids is indicated in Table IV.
Salts
TABLE
IV
SILICIC ACIDS
16. Alkali Silicates.
Commercial sodium
silicate,
known
as water glass, is made by fusing sand, flint, or kieselguhr with sodium carbonate and charcoal, and extracting the
glassy mass in an autoclave, or
by dissolving the silica in sodium hydroxide. The product has a ratio of SiO 2 to Na 2O, between 2 and 4, and is usually sold in concentrated
solution as a syrupy liquid.
Water glass is used in soaps and washing powders to provide an alkaline reaction. It is used: for fireproofing mapaper manufacturing as sizing; as an eggpreservative; and as a mineral glue for cementing wood, glass, porcelain, etc. Solid sodium metasilicate, Na 2 SiOa
terials;
in
5H
ers
O, orthosilicate, Na4SiO4
and "sesqui"
silicate
Na 8-
HSiO4 -5H 2 O
are commercial products, used as water softensilicates
and cleaning agents.

resemble the sodium compound.
The other alkali
318
REFERENCE
[Ch.
XIV
Temperature-composition curves for the system, K 2 O SiO 2 H2O, show many hydrates of the salts, 2 SiO3 and K 2 Si 2 O5, and lithium forms the ortho salt, Li 4 SiO 4 Although silica
is
soluble in concentrated
ammonia,
solid
ammonium
sili-
cates cannot be prepared, as the solutions hydrolyze

pletely
17.
com-
when evaporated.
Mineral Silicates and Rocks. The solidification of the earth's molten magma has produced the igneous rocks. The action of wind and water has tended to break them up or partially dissolve them and to deposit the products as the sedimentary rocks. The latter have frequently been buried and subjected to considerable heat and pressure and
thus changed in form. The products of this process are the metamorphic rocks. New flows of molten magma have occurred and these have produced changes in the adjacent rocks (contact metamorphism). The igneous rocks have
generally crystallized with the separation of materials of more or less definite composition, the silicate minerals
Table V) and a general classification of the igneous may be made on the basis of the kinds of minerals which are present. There are so many possible combina(cf.
rocks
tions of the primary minerals that classification is difficult and many miscellaneous types are found outside the more
common
groupings. Also in any class of rocks with the same general composition there are large variations in apIf the pearance because of differences in crystal size. mineral grains are large enough to be seen by the unaided The fine-texture eye, the rocks are called granitoid.
rocks are f elsitoid. In some cases there are large crystals in a fine-grained ground mass and the rock is known as porphyry. Rapid cooling may result in the formation of a non-crystalline solid or glass. Thus granite is granitoid, the f elsitoid form
is
rhyolite, intermediate is granite

is
porphyry and a common
The names of the common rock families given below are the names of the granitoid form followed by the name of the felsitoid, e.g., Granite Rhyoglass form
obsidian.
17]
SILICON
319
TABLE V
MINERAL SILICATES
Important Primary Minerals
(Orthoclase, KAlSi 3 O 8 (monosymmetric) KAlSi 3 O 8 (anorthic) Acid plagioclase, Albite, NaAlSi 3 O 8 (Basic plagiociase, Anorthite, CaAl 2Si 2O 8
fLeucite,
I
Feldspars
JMicrocline,
I
KAl(SiO 3 ) 2
Feldspathoid group
Nepheline, [Na, K]AISiO 4 ISodalite, Na 8 Al 6 Cl 2 (Si 6 O2 4 )

[Lazurite, Na5Al 3 S(SiO 4 ) 3
Enstatite,
MgSi0 4
Pyroxene
(Cleavage 87
and 93)
Amphibole
(Cleavage 56
Hypersthene, [Mg, Fe]SiO 3 Diopside, Ca[Mg, Fe](SiO 3 ) 2 Augite, CaMg(Si0 3 ) 2 [Mg, Fe][Al 2 O 3 Fe 2 O 3 ](SiO 8 )
Jadeite,
NaAl(Si0 3 ) 2
<
(Anthophyllite, (OH) 2 (Mg, Fej 7 Si 8 O 22 Tremolite, (OH) 2 Ca 2 Mg5(Si 4 On) 2
and 124)
[Hornblende, Ca(MgFe) 3 Si 4 Oi 2
NaAlSi 2O 6
Mica
Muscovite, (OH) 2 KAl 2 Si 3 AlOio Biotite, (OH) 2 K(Mg, Fe) 3 AlSi 3 O 10

Phlogopite,
Lepidolite,
(OH) 2 KMg 3 Si 3 AlO 10 KLi 2 Al(Si 4 Oio)(OH, F) 2
Olivine group
fOlivine,
\Forsterite,
(Mg, Fe) 2 SiO 4 Mg 2SiO 4
Minor Rock-making Minerals

Titanite,
CaTiSiOs
Silicates of less
abundant elements
Be 3 Al 2 (SiO 3 ) 6 Spodumene, LiAl (8103)2 Calamine, Zn 2 (OH) 2 SiO 3 Willemite, Zn 2 SiO 4

Beryl,
Zircon, ZrSiO 4
Tourmaline, (Na 2 Ca)(Mg, Al^BgShsHxOga Topaz, (AlF) 2 SiO 4
Secondary Minerals
Heulandite,
Zeolites, derived
from
Stilbite,
(Na 2 Ca)Al 2 Si 6O 16 '6H 2 O
feldspars and feldspathoids
Chabazite, [Ca,
Na 2 ]Al
(SiO 3 ) 4 -6H 2O
Analcite, NaAl(SiO 3 ) 2 .H 2 O Natrolite, Na 2 Al 2 Si 3 Oio-2H20

6 Si 3 Alio(OH) 8 Clinochlore, Al, Epidote, Ca 2 (Al, Fe) 3 OH(Si0 4 ) 3 6 (Al, Fe)(Al, Si) 4 Oi Penninite, 3 (Si 4 lo )(OH) 2 Talc,
Mg
Chlorite
Mg
Mg O
(OH) 8
and
other hydrous
silicates resulting
<
(Serpentine, Kaolinite.
2H 2O-3MgO-2SiO 2
320
REFERENCE

TABLE V
(Confd)
[Ch.
XIV
MINERAL SILICATES
Grossularite,
Garnet
v
Almandite, Fe 3 Al 2 (SiO 4 )3 Pyrope, Mg 3 Al 2 (SiO4) Andradite,
and
'Andalusite, Al 2 SiO 5
Cyanite, Al 2 SiO5
other silicates resulting mainly from
Sillimanite, Al 2 SiO 5
metamorphism
Prehnite, HiCaa Scapolite, Ca4Al 6 Si 6
4(SO4,
CO
3)
to
Vesuvianite, Cai Al 4 (Mg, Fe) 2 Si 9 O34(OH) 4 Wollastonite, CaSiO 3

lite
family.
is
In the
first
quartz may be considered as an acidic rock because of the high percentage of the acid oxides. On the other hand peridotite is basic.
present but
it is
three families listed, the mineral absent in the others. Granite
IGNEOUS ROCKS
Minerals: orthoclase and quartz, Granite Rhyolite. with or without acid plagioclase, muscovite, biotite and hornblende. Average per cent SiO 2 70. Glass forms:
,
obsidian, pumice.
Granite diorite
clase with smaller
Quartz
latite.
amounts
of orthoclase
or without biotite hornblende, cent SiO 2 65.

,
Minerals: acid plagioand quartz with pyroxene. Average per
Quartz diorite Dacite. Minerals: plagioclase, quartz with biotite or hornblende or augite. Average per cent
SiO 2
64.
plagioclase, hornblende, with or without biotite, augite, orthoclase. Average per cent SiO 2 60. Glass forms: Andesite obsidian. Minerals: orthoclase, hornblende, Syenite Trachyte. with or without biotite. Average per cent plagioclase,
:
,
Diorite
Andesite.
Minerals
SiO 2
61.
Nephelite
syenite
Phonolite.
Minerals:
orthoclase
17]
SILICON
321
plagioclase,
55.
nephelite,
hornblende
biotite, sodalite, leucite, augite.
with or without Average per cent SiO 2

,
Minerals: Augite, olivine, basic plagioclase biotite, hornblende. Average per cent SiO 2 49. Glass forms: tachylite. Peridotite. Minerals: pyroxene, olivine, hornblende,
Basalt.
,
Gabbro
Average per cent SiC>2, 38. Granite is the most abundant igneous rock in the earth's crust, indeed the continents appear to be slabs of granite about 20 miles thick "floating" on heavier basaltic mabiotite, magnetite.
very probable that the composition of the major portion of the earth, i.e., the mantel extending down to the iron core, is similar to
nearly that
of
terial.
The composition
of the stony meteorites
is
peridotite
and
it
is
peridotite which consists largely of magnesium and iron There is considerable evidence to support orthosilicates.
the theory that the earth was condensed from a cold cosmic In the initial state the outer layer was basaltic in After about a billion years the radioactivity character. 40 ) generated sufficient heat to start the decom(largely
cloud.
position of the basalt into granite, which rose to form continents, and dunite (heavy orthosilicate) which sank.
appears probable that this process that the continents are growing.
It
is still
continuing and
TABLE
VI
APPROXIMATE AVERAGE COMPOSITION OF VARIOUS IGNEOUS ROCKS
322
REFERENCE
[Ch.
XIV
18. Weathering. The primary minerals disintegrate under the mechanical and chemical action of the wind and rain. Large quartz crystals are broken down into small
The feldspars are decomposed by the grains of sand. action of carbon dioxide and water into sand and clay:
2KAlSi 3 O 8 + H 2 CO 3 + H 2 O = K 2 CO 3 + H 4 Al 2 Si2O9 + 4SiO 2 Under other conditions bauxite, hydrous alumina, is formed. Another product is a fibrous type of muscovite: 3KAlSi 3 O8 + H 2 CO 3 = KH 2 Al 3 Si 3 O 12 + 6SiO 2 + K 2 CO 3 Plagioclase alters into the zeolites and related mineral, and biotite forms chlorites. Olivine is readily attacked by carbonic acid and oxygen; the iron is oxidized and deposited as magnetite and the magnesium forms magnesite. The pyroxenes and amphiboles undergo somewhat similar
.
changes.
Sedimentary and Metamorphic Rocks. The common sedimentary deposited products are clay, shale, sandstone, limestone, dolomite, magnetite and gypsum. Under metamorphic conditions sandstone may become flint or quartzite. Shale may be converted to slate and limestone to marble. Contact metamorphism produces complicated not only in the rocks into which the intrusion changes takes place but also in the intruded molten mass. The micas, muscovite 19. Uses of Common Minerals. and phlogopite (amber mica), are used ex(white mica)
tensively in the electrical industries as insulating materials. striking characteristic of these minerals is their cleavage
into very thin elastic transparent sheets.
Mica
is
used in
lamp chimneys, as Christmas tree "snow," as a decorative material for wall paper, and The term asbestos includes all in many special paints.
making windows for
stoves, in
minerals having a fibrous structure. The most important are some of the amphibole minerals, e.g., anthophyllite and fibrous serpentine. These minerals have a fibrous
structure, silky luster,
is
and are difficultly fusible. Asbestos important commercially as a thermal insulator. The
20]
SILICON
323
long fibers permit the manufacture of asbestos yarn, cloth, and paper, and from these innumerable fireproof objects. Mixtures of asbestos and Portland cement are used in
fireproof shingles.
num
Kaolin, impure kaolinite, or clay, silicate, and talc, or soapstone,

silicate.
is
used in soap, French chalk, talcum powder; and in paint, roofing, and rubber. A fibrous form is used extensively in paper. Soapstone is used as a refractory material. The bentonites and the pyrophillites are forms of aluminum silicates or the clay minerals. Both are important as commercial fillers for rubber, paper, and soaps. Feldspar is employed most extensively in the glass and ceramics industries. It is also used to cover cement and tarred surfaces to give them the appearance of granite. 20. Structure of Silicate Minerals. The tetrahedron of oxygen atoms with a silicon at the center, which occurs in silica (Par. 14), is a general characteristic of all silicate minerals. In the orthosilicates such as zircon, ZrSiO 4 and olivine, (Mg, Fe) 2 SiO 4 the crystal is a lattice of SiO 4 tetrahedra and the positive ions; and the same is true of the 6 orthodisilicates, the negative ion, Si2C>7~ consisting of two tetrahedra linked by a corner. The metasilicates (SiOs radical) may complete the tetrahedron of oxygen atoms by
,
,
sium Talc
Clay
is
a hydrated alumia hydrated magnefurther discussed under pottery.

is
is
. tive ions with the ring-like negative ions Si 6 Oi 8 three membered ring is also known in benitoite, BaTiSisCV In the pyroxenes, e.g., CaMg(SiO 3 )2, which are also meta-
in which two corners of each tetrahedron are most common ring contains six tetrahedra, for shared. The example beryl, Be 3 Al 2 Si 6 Oi8, consists of a lattice of the posi~ 12
forming rings
silicates,
rings,
the SiO 3 groups form infinite chains instead of and the positive ions serve to bind the chains tocontain infinite double chains
gether.
The amphiboles formed from the Si 4Oir6
in Fig. 5.
These are illustrated groups. In the various types of asbestos these chains
324
REFERENCE
[Ch.
XIV
are in bundles of parallel fibers. In other cases they form sheets of matted fibers. Jade appears to be a mineral in which the fibers are matted in all directions.
4 Silicates containing the Si 4 Oio~~ group (or AlSi 3 Oi Si is replaced by Al) form infinite sheets of silicon "" 5
one oxygen
if
tetrahedra. These may be looked upon as two dimensional extensions of the arrangement shown in Fig. 5 to give a sheet with the appearance
of
a wire netting.
Such
held together by positive ions are found in

sheets
the clay minerals. Double sheets with the vertices of

the
FIG.
5.
tetrahedra
pointing
toward each other occur In the former the sheets are in the mica minerals and talc. held together by alkali or alkaline earth ions, but the latter contains no intermediate atoms. In the chlorite the micalike
Chains
in the amphiboles.
sheets
are
separated
layers.
by intermediate magnesium-
aluminum oxide
Silica
has been given as an example of a three-dimensional network of silicon-oxygen tetrahedra. If one out of every four silicons in the structure is replaced by KA1, the resulting feldspar, e.g., KAlSi 3 Os, is a network of SiO 4 and A1O* The negative charge is neutralized by the potetrahedra. tassium ions which occupy holes in the structure. In addition to the feldspar group the zeolite minerals have a three-dimensional framework. These structures are, however,
large cavities and channels. They are of holding large amounts of water which may be capable driven off readily, and the positive ions which are contained
in the cavities
more open with
and balance the negative charge on the framework are readily replaceable by other ions. 21. Pottery and Porcelain. Mixtures of clay (kaolinite), quartz, and feldspar, in various proportions and baked at various temperatures, form an extensive series of ceramic
22]
SILICON
325
Most types of pottery or bricks are made products. from naturally occurring clays, which contain sand and They are usually colored buff or red by iron feldspar.
oxide, the white porcelain clays being relatively scarce. Upon heating, kaolin is altered, probably losing water,
according to the equation: 4~2H 2 O; and around 1200
Al 2 Si 2 O9 = Al 2 SiO 5 SiO 2 the feldspar fuses and serves

4
to bind the clay and quartz together. The properties of the earthenware depend to a great extent upon the temperature at which it is baked, and there is often but slight variation in composition between different types of products. Soft porcelain contains a high per cent of calcium phos-
phate. Glaze is imparted to the cheaper grades of pottery by the introduction of sodium chloride near the end of the firing. Other glazes used are fusible lead calcium alumino-borosilicates, or, in many cases, simple feldspar. Glass is a fused non-crystalline mixture of 22. Glass.
basic oxides and silicon dioxide.
The
basic oxides are
usually the alkalies and alkaline earths, but they may be substituted in whole or in part by oxides of lead, zinc, arsenic, antimony, aluminum, etc.; and the silicon dioxide
by
boric or phosphoric oxides.
Like
all
super-cooled liquids,
glass does not have a definite melting point, but softens gradually over a range of temperatures. In this viscous
may be blown or rolled into almost any desired or form. The raw materials which are fused together shape to form glass are sand, or the other acid oxides, and generally the carbonates of the basic constituents.
state, glass
The manufacture
of
represented by the equation,
CaSi 6 Oi5 + 3CO 2 but the product cannot be considered as a definite compound. It is used in making bottles,
4
,
= Na
common soda glass 2Na CO 3 + CaCO 3

2
is
often
6SiO 2
window
The percentage comglass, glass tubing, etc. of soda glass is approximately: SiO 2 71-78; Na 2 O, position
,
12-17; CaO, 5-15; A1 2 O 3

glass, also called
1-4.
hard
glass,
The corresponding potash or Bohemian glass, has a
326
REFERENCE

TABLE
VII
[Ch.
XIV
PERCENTAGE COMPOSITION OF VARIOUS GLASSES
Potash-lead glass, or flint higher fusing temperature. has a high density and index of refraction, and is glass, used in making cut glass articles. Pyrex glass is very high in the acid oxides: SiO 2 80 per cent, B 2 O 3 12 per cent, with the balance Na 2 O and A1 2 O 3 It has a low coefficient of
,
is, therefore, very suitable for articles subto sudden changes in temperature. It is also resistject ant to chemical action. Jena glass is a zinc-barium boro-
expansion, and
silicate.
Si+ 4 ions in a crystal may be replaced by the combinations A1+ 3 P+ 5 or B+ 3 P+ 5 Thus A1PO 4 has a crystal structure which resembles that of cristobalite. This
.
Two
principle has been utilized in the development of phosphate glasses which are chemically resistant to the action of hydrofluoric acid.
be colored by the presence of small amounts chromium or copper giving green; cobalt, blue; manganese, violet. A colloidal metal suspension of gold gives ruby glass. "Milk glass' usually contains stannic oxide or calcium fluoride.
Glass
may
of metal oxides:
'
If glass is held at a high temperature for a long time, a certain amount of crystallization may occur (called devitri-
fication).
Thick glass objects must be carefully annealed,
24]
SILICON
327
i.e.
cooled very slowly, as the cooling of the outer portions
more rapidly than the interior will result in great strains and the subsequent cracking of the object. 23. Portland Cement. Although lime mortars have been used for centuries, the modern hydraulic cement dates back only to about 1825, and its extensive use to about 1900. The approximate composition of Portland cement
is
given in Table VIII.
TABLE
VIII
COMPOSITION OF PORTLAND CEMENT
Cement
is
made by heating
a mixture of limestone and
clay, or material of equivalent composition, to the point of incipient fusion (about 1450 C.). The product, termed
is ground with 2-3 per cent of gypsum, added to decrease the time of setting, to give the cement. The chemical composition appears to be a solid solu-
clinker,
tion of approximately
two moles of Ca SiO and one of Ca 3 (AlO 3 ) 2 although considerable Ca 3 SiO 5 may also be present. The Ca2SiC>4 and CasSiOs hydrolyze with water, Ca 2 SiO 4 + H 2 O = CaSiO 3 + Ca(OH) 2 and the strength
2 4
,
of the set
cement
is
due to the
Si
Si
bonds
of the
CaSiO 3 chain
structure.
conversion of the function of the calcium aluminate appears to be the lowering of the point of incipient fusion. The production of cement in the United States in 1948
.
The initial setting is aided by the Ca(OH) 2 into CaCO 3 The principal
was about 175 million barrels. The major portion of this was used in mixture with crushed rock and sand to make
concrete.
The 24. Organo-silicon Polymers. bon and silicon is relatively strong.

phenyl, Si(C 6
5 )4,
is
a crystalline
bond between carThus silicon tetrasubstance which distills
328
REFERENCE

and
[Ch.
XIV
at red heat without decomposition
silicon tetramethyl,
51(0113)4, can be shaken with concentrated sulfuric acid without reaction. Organo-derivatives of Si(OH) 4 can be
prepared by the hydrolysis of the organo-silicon chlorides. Thus dimethyldichlorsilicomethane hydrolyzes, (CH 3 ) 2 SiCl 2 + 2H 2 O = (CH 3 )2Si(OH) 2 This ester polymerizes to give chains having the structure,
.
CH
These organo-silicon polymers are called silicones from analogy of the (CH 3 ) 2 SiO group to acetone, and the general name is now used for all materials having C Si O bonds.
Cross linkage of linear chains may be obtained by the simultaneous hydrolysis of a disubstituted silicon chloride with a monosubstituted compound or with carbon tetrachloride.
RSi(OH) 3
+ R Si(OH) =
2
2
Si(OH) 4
+ R Si(OH)
2
or "rubber"-like plastics.
be obtained as short chain oils oils have very small variations of viscosity with temperature and remain fluid to 80 C. Their uses include high temperatures as low as
silicones
The methyl
may
The
$ 26]
SILICON
electrical insulations,
329
temperature
low temperature lubri-
cation and heat-resisting greases. The elastomers may be " compounded to rubbers" that do not decompose at 300 C. 55 C. nor harden at They are employed as gasket
materials for high temperature operation. In addition to the methyl derivatives, polymers of ethyl and phenyl
radicals are also prepared.
methylchlorosilicones as vapors react with hydrophilic surfaces to give a film which is essentially a thin Such surfaces are highly watercoating of a silicone. Wood, cotton and glass surfaces are readily repellent.
The
coated and by special treatment certain metallic surfaces may also be coated. This process for metals is the basis for the development of cooking utensils which require no
grease. 25. Silicon
and
Sulfur.
.
Silicon burns in sulfur
vapor to
form the
The structure of the solid is disulfide, SiS 2 infinite chains of SiS 4 tetrahedra sharing opposite edges:
VVVV /\/\/\/\/
S
Si
Si
Si
Si
The
sulfide.
sulfide hydrolyzes in water to silicic acid and hydrogen the sulfide is fused with alkali sulfides,
When
thiosilicates are formed, e.g., Na 2 SiS 3 26. Silicate Analysis. In detecting the presence of silicon, advantage is taken of the volatility of silicon tetra.
The sample is heated with hydrofluoric acid in a lead or platinum dish. If silicon is present, a drop of water in a wire loop, placed in the fumes, becomes cloudy owing
fluoride.
to the formation of
silicic
acid: 3SiF 4
+ 3H O = H
2
SiO 3
2H
SiF 6
determined quantitatively by gravimetric methods, generally separating silicon dioxide and weighing as such. In this process, decomposition of the silicate
Silicates are
330
REFERENCE
[Ch.
XIV
may often be accomplished by digesting with concentrated hydrochloric acid, leaving a residue of silica. Other silicates must first be fused with sodium carbonate before
they can be decomposed by acid. The silica residue may be contaminated with BaSO 4 A1 2 3 Fe 2 O 3 TiO 2 and
, ,
,
,
oxides of certain rare elements; the amount in the mixture is often determined by heating with hydrofluoric acid,
obtaining the silica by loss of weight, due to the volatilization of the tetrafluoride.
Chapter
XV
THE METALS OF GROUP IV. TITANIUM, ZIRCONIUM, HAFNIUM, AND
GERMANIUM,
1.
TIN,
LEAD
and
and second elements of Group IV, carbon have been discussed in the two preceding chapters. The remaining elements of the main group are titanium, zirconium, and hafnium, and of the subgroup, germanium, tin, and lead. All of the free elements are metals, but both branches of the group show many simifirst
The
silicon,
larities to silicon in their
chemical properties. of the main group the second elements of a transition series in which are each the kernel is being transformed from the noble gas structure to the eighteen electron type (Append. XVIII). However, the two d electrons are easily removed so that all members of the group show the characteristic + 4 oxidation Titanium has also a fairly stable + 3 and a less state.
Titanium and the heavier elements
stable
+
4
2 state.
states, the
and
of both the + 2 former becoming increasingly stable with respect to the latter with increasing atomic weight.
The subgroup elements form compounds
The
tetroxides of
all
the elements, are amphoteric, and
those of the main group are, in general, somewhat more basic than the oxides of the corresponding elements of the
subgroup, which
of the
agreement with a slightly larger size ions, and in both groups the basic character increases with increasing size. Like silicon, all
is in
main group
331
332
REFERENCE

form complex
[Ch.
XV
of the
all
members
of the group
fluorides,
and
the tetrachlorides, except thorium, are volatile liquids. One of the most striking differences between the two branches of the group is the much greater stability of the sulfides of germanium, tin, and lead. This stability of the
sulfides is a general characteristic of the ions with eighteen electrons in the outer shell of the kernel (cf. VII 2). The
elements of Subgroup IV resemble those of Subgroup III in not forming complex ions with ammonia. Cerium and thorium are often discussed in connection with Group IV, but the former should be included in the rare earths, the latter with the actinide series although in many respects their chemistry resembles that of zirconium and hafnium.
TITANIUM, ZIRCONIUM,
2.
AND HAFNIUM
The elements of this group are by no commonly been considered. Titanium ranks eighth among the metals in order of abunOccurrence.
means
as rare as they have
dance
is
in the igneous rocks, the per cent of the element present in the earth's crust being estimated at 0.43, and
the fourth most abundant metallic element.
The values
for the other elements of the group are: zirconium, 0.026; and hafnium, 3 X 10~ 5 Zirconium is more abundant than copper, zinc and lead combined. The elements do not occur free, but their compounds
.
in chemical behavior
are widely distributed in nature. Because of the similarity between these elements and silicon,
their presence in rocks
often overlooked. The most important titanium ores are ilmenite, FeTiO 3 and rutile, TiO2. There are various related ores such as
is
,
arizonite,
Fe 2 O 3 -3TiO 2
Metatitanates of
ferric iron, cal-
cium, magnesium, manganese, and lead, also occur. Titanosilicates such as sphene, CaTiSiO 6 are common, and less frequently borotitanates and titanoantimonates. The
,
2J
THE METALS OF GROUP IV
333
American production of the oxide is around 150,000 tons, largely from the deposits of ilmenite in New York, and an
additional 250,000 tons are imported. The sand of certain beaches in India is the principal foreign source. The major portion is consumed in the manufacture of white pigments.
Zirconium occurs principally as baddeleyite, ZrO 2 and The domestic consumption of the dioxide zircon, ZrSiO 4 Of this, 3,000 tons are obtained is around 30,000 tons. from Florida sand dunes and the balance imported from
,
present to the extent of primary zirconium minerals. Metals. The electro-positive nature of the ele3. The ments, together with the high melting point of the oxides
Brazil
1
is
and Australia.
Hafnium
all
or 2 per cent in practically
and the tendency to form carbides,

difficult.
nitrides,
and
silicides
at high temperatures, renders the preparation of the metals
gives contains 5 or 6 per cent aluminum, but if iron is present, the product is largely ferro-titanium. Zirconium may be
The Goldschmidt reduction with aluminum aluminum alloys. In the case of titanium, the alloy
separated from the aluminum alloy by distillation. The reduction of titanium dioxide by carbon in an electric furnace yields a mixture of the metal and carbide. Ferrocarbontitanium is made by the reduction of mixtures of
iron
and titanium oxides.
Both titanium and zirconium are
produced commercially by the reduction of the tetrachloride by magnesium in an atmosphere of helium around 800900 C. In the case of titanium, the excess magnesium metal and chloride is removed by dilute acid while with zirconium these products are volatilized out under vacuum The metals are ground, the powder highly at 900 C. and cintered at about 1000 C. compressed Titanium metal is silver white. It may be rolled and cold worked, is lighter and stronger than steel, and has excellent corrosion resistance. The metal surface oxidizes or nitrides with ease and may thus be surface hardened. The properties of zirconium are similar and in addition
334
REFERENCE
is
[Ch.
XV
the metal
highly resistant to corrosion

.
by concentrated
The metals titanium, zirconium, HC1, HNO 3 or H 2 SO 4 and hafnium appear to have the hexagonal close packed form of crystal lattice, but titanium changes to a body centered cubic above 880 C.
TABLE
I
ATOMS AND PHYSICAL PROPERTIES
If
the price of titanium can be reduced,
it
promises to
become most important as a structural material. At the present price of $4 per pound it can replace many special steels and aluminum bronze for light objects. Ferrotitanium is used extensively in the steel industry the titanium
;
considered extremely valuable in removing nitrogen (by forming nitride) from, and in imparting toughness to, steel. Ferrozirconium is an excellent scavenger for oxygen and sulfur and also improves the grain size in steel. Zirconium should replace tantalum in radio tubes, electric condensers
is
and as a non-corrosive metal for pipes, tank linings and chemical uses. 4. Reactions of the Metals. The reactions of the metals
are summarized in Table
II.
they are not very reactive, oxygen or by hydrogen ion.
At ordinary temperatures, being oxidized but slowly by Measurements of the electrode
6]
335
potentials of the group are unreliable because of the

culties in obtaining equilibrium conditions.
diffi-
In spite of
its
TABLE
REACTIONS OF
II
Ti, Zr,
AND Hf
M M M M M M M
+ Oz = MO2 + 2X = MX + 2H O = MO + 2H + 4HF = MF + 2H + 4HC1 = MC1 + 2H

2
2 4
2 4
Burn when heated With halogens when heated With steam
With hot concentrated

TiCl 3
acid,
but Ti gives
+H + 2S
= =
2
MH
MS
2
3M + 2N = M N M +2H 2O = MO +4H+ +
3
TiH 2 doubtful. Slow with Zr and Hf Also react with P, C, B, and Si at high temperatures Also
MN
4<r
Potential
in
volts,
Ti,
0.86;
Zr,
1.43;
Hf, 1.57
highly electropositive character zirconium

soluble in nitric acid.
is
not readily
TITANIUM COMPOUNDS
Oxidation States. Titanium forms compounds in which it has the oxidation states of +2, +3, and + 4.
5.
Important oxidation-reduction potentials relating the states

are given below:
VOLTS
Ti = Ti ++ 2e~ Ti + + = Ti +++ c~ H 2O Ti+ ++ - TiO+ + 4- 2H+ 6F~ Ti - TiF 6 4c~
1.63 0.37
+ +
+ er
co-0.1
1.19
6.
The
2 State.
high temperature magnesium, or titanium.

oxidized in solution
oxide, TiO, is prepared by the reduction of the dioxide by carbon,
The
by
centration
very low. high temperatures by the decomposition of the trichloride 2TiCl 3 = TiCl 2 TiCl 4
is
but its salts are readily ion unless the acid conhydrogen The dichloride may be formed at
It is basic,
:
.
336
REFERENCE
BOOK OF INORGANIC CHLMISTRY
[Ch.
XV
sesquioxide is It 2 O. The corresponding titanous hydroxide, also is basic. Ti(OH)s, is precipitated upon the addition of alkalies to
7.
Compounds
of the
3 State.
The
formed
in the reaction:
2TiO 2
+H =
2
Ti 2 O 3
+H
titanous salts in solution.
reducing agent
dioxide:
(Par. 5).
This hydroxide is a very powerful It evolves hydrogen to form the
Ti(OH) 3 = TiO 2
+HO+
2
trate in alkaline solution to

3
= NH + 8TiO 2 + OH" + may be prepared by reducing

from solutions of titanic
salts
~ ammonia: 8Ti(OH) 8 + NO 3 10H 2 O. Anhydrous trihalides

the tetrahalides at moder-
^H
and reduces
ni-
ately high temperatures, e.g., ~ Solutions of titanous ion, Ti~M +
TiCl 4
+
,
Ag = TiCl 3
AgCl.
by
are readily prepared electrolytic reduction, or
by the reducing action of zinc upon the hot solution. Titanous solutions are violet. Titanous solutions are important as volumetric reagents, as they are oxidized quanti4"^ and 4~~, tatively by many oxidizing agents, e.g., Fe Titanous ion is much less hydrolyzed than the titanic ion.
MnO
The formation
of the slightly soluble hydroxide has been
discussed above.
The cesium titanous alum, CsTi(SO 4 ) 2 12H 2 O, is but sparingly soluble. 8. Compounds of the + 4 State. The dioxide occurs
nature in two tetragonal forms, rutile and anatase, and also in a rhombic form called brookite. The pure oxide is white, but natural rutile is usually brown or black. The arrangement of the atoms in the rutile crystal lattice is given in Appendix V. This is the common crystal form of to 2 when the ratio of the diameter of compounds
in
MX
X
is
is
<
0.6.
When
this ratio is greater the
arrangement
generally that of fluorite. The fused oxide is difficult to dissolve, but the hydrated forms dissolve readily in acids and slightly in alkalies. However, the chemistry of the titanium minerals is essen-
tially that of
an acid oxide. The oxide fused with metal oxides or carbonates yields titanates, e.g., CaTiO 3 Ba 2 Ti 3 O 8
,
ZnTiOs,
Zn 2 TiO 3
PbTiO 3
Mn
TiO 4
The potassium
9]
337
2 TiO 3 metatitanate, boiling, the titanium
is
is
soluble in cold water, but upon completely precipitated as the
The dioxide has become one of the most imwhite pigments, the annual domestic consumption portant for this purpose being close to 400,000 tons. The pigment is made by hydrolysis of Ti (804)2 and possesses both good covering power and chemical inertness. The dioxide is used in ceramics to make a yellow glassware. The hydrous
dioxide.
oxide
hydrolysis of the tetrachloride is an immordant. portant When an acid solution of a titanium salt is made alkaline, a hydrogel is formed. Upon aging, the gel gives an
made by
X-ray pattern corresponding to that of anatase. Hydrous oxide formed by the hydrolysis of TiCl 4 appears to be the rutile modification. The precipitated gel, often referred to as ortho- or ^-titanic acid, is readily soluble in acids. Socalled meta- or ^-titanic acid, an insoluble form, is obtained by the action of nitric acid upon the metal. (Cf. similar
stannic acids.) Rutile is also of considerable importance in the manufacture of welding rods, in the production of titanium carbide
for cutting tools
and as a high
dielectric material.
The
dielectric constant of rutile is 173 parallel to the principal axis and 89 perpendicular to the axis. The dielectric con-
stant of preparations of CaTiO 3 is as high as 20,000. The addition of hydrogen peroxide to a solution of the sulfate yields the complex orange peroxy ion TiO 2 (SO 4 )2
The
peroxy-acid, H 4 TiO 5 has been precipitated from ammonia solutions and the salt K 4 TiO 8 is known. 9. The anhydrous halides are prepared by direct reaction of the elements, or by the action of the halogen upon heated mixtures of the oxide and carbon, e.g., TiO 2 + C + 2C1 2 = TiCl 4 + CO 2 Water solutions are prepared by dis.
solving the hydrated oxide in concentrated hydrohalic acid, but in dilute acid the halides readily hydrolyze to the dioxThe tetrachloride is employed for producing smoke ide.
338
REFERENCE
[Ch.
XV
screens.
The smoke particles are largely TiCl 4 -5H 2 O. The and Tide halides form complex ions, e.g., TiFe lighter
.
,
Potassium fluorotitanate, K 2 TiF 6 is but 10. The hydrated dioxide dissolves in

tions.
slightly soluble. sulfuric acid solu-
In dilute acid, the sulfate hydrolyzes to form basic sulfates, e.g., Ti 2 O(SO 4 ) 3 '3H 2 O and TiOSO 4 -nH 2 O. Similarly basic nitrates and phosphates exist, and the phosphates form a number of double basic compounds, e.g., potassium
titanyl phosphate, K(TiO)PO 4 The addition of soluble sulfides to titanium solutions

.
results in the precipitation of the dioxide,
but the sulfide
be formed by heating chloride and hydrogen sulfide 2H 2 S = TiS 2 + 4HC1. The sulvapors together: TiCl 4 At fide does not form polysulfides with alkali sulfides. the element unites with sulfur, forming high temperatures, TiS and Ti 2 S 3
may
ZIRCONIUM COMPOUNDS
Zirconium forms the dioxide and possibly two oxides of lower oxidation states, but the evidence in favor of these is of doubtful nature. The dioxide occurs in nature as the mineral baddeleyite. Like titania, it reacts with fused hydroxides and carbonates, forming insoluble zirconates, e.g., Na 2 ZrO 3 CaZrO 3 PbZrO 3 The oxide is widely used in ceramics as a constituent of enamels. Zircon refractories are finding increasing use in steel mills since zirconium oxide has a melting point of 2950 C. or about twice that
11.
,
,
of steel.
The hydrated
oxide,
,
usually regarded as zirsalts.
conium hydroxide, Zr(OH) 4
is
formed as a hydrogel upon
the addition of alkali to solutions of zirconium
The
hydroxide is readily soluble in acids and somewhat soluble in cold concentrated alkali, with which it reacts mainly to form insoluble zirconate. Hydrogen peroxide reacts with
the hydroxide to form the hydrated peroxide, probably In sulfuric acid solution the complex peroxysul4 ZrO 5 fate, O 2 ZrO 2 SO 4 ZrO 2 appears to be formed.
3]
339
The
and methods
tetrahalides resemble those of titanium in properties of formation. Basic halides are obtained upon
e.g.,
evaporation of the water solutions of the halides,

zirconyl chloride,
ning.
ZrOCl 2
The
latter is
employed
in tan-
Many
slightly soluble fluorozirconates are
known,
e.g., K^ZrFe, BaZrFe, and also less stable chlorozirconates. Reduction of the tetrachloride with aluminum at 300 yields the trichloride, ZrCl 3 and at higher temperatures, the dichloride, ZrCl 2 but these compounds cannot be formed in water solutions.
,
,
sulfates, nitrates, and phosphates resemble closely the corresponding titanic compounds. The
sulfides,
Zirconium
normal sulfate
are
furic acid solutions,
known.
be crystallized from concentrated suland many basic and double sulfates Hydrogen reacts with zirconium at red heat,
may
apparently forming the unstable hydride, ZrH 2 The naturally occurring silicate, ZrSiO 4 known as zircon or jargon, is valued as a jewel. On account of their luster and hardness (7.5) zircons are employed as substitutes for diamonds. They occur in a great variety of colors, red,
.
,
green, blue,
and white.
HAFNIUM COMPOUNDS
12.
Hafnium resembles zirconium
so closely that the

in the zirconium
presence of several per cent of
hafnium
compounds was not discovered until 1923, although the chemistry of zirconium was carefully investigated during the preceding century. Any compound formed by the one element appears to be formed by the other, and, as a rule, the melting points, boiling points, and solubilities of the two compounds are very similar. Hafnium dioxide and hydroxide appear to be slightly more basic than the zirconium
compounds.
Titanium may be extracted from its ores by alkaline fusion, followed by digestion in acid, or by fusion with potassium acid sulfate and extraction with water.
13. Analytical.
340
REFERENCE
[Ch.
XV
The
addition of hydrogen peroxide to a sulfuric acid solu-
tion of titanium produces the characteristic yellow or orange color of the peroxy-acid. Titanic solutions may be reduced
to the violet
3 state
by
zinc in hot acid solution,
and the
titanium
this solution with
be determined quantitatively by titrating permanganate. Titanium hydroxide is the addition of alkalies, ammonia, and precipitated by soluble carbonates and sulfides to solutions of titanium
may
salts.
acids,
If formed in cold solution, it and somewhat soluble in excess
is
readily soluble in
alkali.
Precipitated
from hot solution, it is not rapidly soluble in acid. Zirconium and hafnium ores may be got into solution by methods similar to those given for titanium. The two elements may be separated from iron, aluminum, beryllium, titanium, and thorium by precipitation from highly acid solutions, as the very slightly soluble zirconyl and hafnyl Alkalies precipitate zirconium phosphates, ZrO(H 2 PO 4 ) 2 and hafnium hydroxides, which are not soluble in excess of
.
the reagent. Ammonium oxalate or oxeilic acid precipitate the oxalates, soluble in excess of the reagents. Separation from iron may be accomplished through the slight solubility of the
potassium complex
fluorides.
per cent of hafnia and zirconia in a sample may be estimated by determination of the density of the oxide mixture. The values for the pure oxides are ZrC>2, 5.73, and HfC>2, 9.68. Hafnium and zirconium are extremely
difficult to
The
separate from each other.
The
greatest differ-
ence in the solubilities of their compounds appear to exist in the citrates, the hafnium salt being the more soluble. Separation may also be carried out through the fractional
precipitation
of
the
phosphates,
oxychlorides,
and the
ammonium and potassium complex fluorides. Separation may also be attained by use of the cation exchange resins
and by solvent extraction of organic complexes. The complex of hafnium with certain diketones is more soluble in
benzene than the corresponding zirconium complex.
14]
THE METALS OF GROUP !V
341
GERMANIUM,
TIN,
AND LEAD
The elements of this group constitute 14. Occurrence. but a very small portion of the igneous rocks, the estimated u 6 and lead, tin, 10~ percentages being germanium, 10~ 2 X 10~ 6 occur frequently in workable They do, however,
,
,
deposits.
Germanium is found in many sulfide ores, especially those of silver, lead, tin, antimony, and zinc. In a number of ores definite sulfide complexes appear to be present, such as Ag 4 GeS 4 and Pb 2 GeS 4 An English coal ash has been re.
The small ported which contains 1.6 per cent GeO 2 domestic supply comes largely from the cadmium fume dust obtained in sintering zinc concentrates. The most important tin mineral is the oxide, SnO 2 called
. ,
Deposits of cassiterite in Cornwall, England, were worked as early as 1000 B.C. by the Phoenicians. The principal sources of the metal at present are mines in the Malay States, Bolivia, and the Dutch East Indies. Tin also occurs as complex sulfides, e.g., SnCu 2 -FeS 4 Pb 6 Sn 2 -Sb 2 Si 2
cassiterite.
,
TABLE
III
ATOMIC AND PHYSICAL PROPERTIES OF GERMANIUM, TIN, AND LEAD
342
REFERENCE
[Ch.
XV
and AggSnSe, and as complex oxides, e.g., CaSnO 4 (BO) 2 and CaO'SnO 2 '3SiO 2 '2H 2 O, but these minerals are of slight importance. The principal lead ore is the sulfide or galena, PbS, and this is generally associated with sulfides of silver, copper,
arsenic,
are cerussite, PbCOs, to have been formed
tin. Other common ores and anglesite, PbSC>4, which appear by the weathering of sulfide ores. Complex oxides and oxychlorides of the metals of Groups V and VI also occur.
antimony, bismuth, and
15. Metallic
Germanium.
The metal may be prepared

by
by reduction
of the dioxide with carbon at red heat, or
the reduction of the oxide or sulfide by heating with potassium cyanide. A metallic copper compound, Cu 3 Ge, may be electro deposited from aqueous alkaline cyanide
solutions, and the metal may be deposited from solutions of Gel 4 in ethylene glycol and from a fused borax elec-
trolyte in
which the dioxide
is
dissolved.
Germanium
is
It forms greyish-white metal, rather hard and brittle. good tarnish resisting mirrors. X-ray data for the solid
indicate that the

structure.
atoms are arranged

is
in a modified
diamond
a "semi-conductor" and is emin radar for the rectification of microwaves. The ployed copper compound has high chemical resistance and may become a useful bronze. 16. Tin. Cassiterite is easily reduced to the metal by C smelting with carbon in a reverberatory furnace SnO 2 = Sn CO 2 The liquid metal is drawn off from the fur:
The metal
The greatest difficulty in the the purification of the ore before smelting. metallurgy This is carried out by roasting, to remove sulfur and arsenic, and if tungsten is present, the ore is fused with sodium carbonate and the tungsten extracted with water. The crude metal usually contains some compounds of iron and
nace and cast into molds.
is
arsenic,
which
may
ingots (liquation), as the
be removed by carefully melting the compounds melt at temperatures
16]
343
somewhat higher than the pure metal. The annual production of tin is about 170,000 tons. Considerable tin is recovered from scrap metal. In the case of tin cans, the recovery is effected by boiling the scrap in a solution of NaOH and NaNO 3 The sodium stannate obtained is then reduced electrolytically to the metal. Tin exists in three solid forms, with definite transitions as summarized in the following scheme:
.
18
161
Sn/3
232
(liquid)
Sna =
= Sn7 = Sn
The a-form
white tin to /3 50 the transformation is complete in a few ture, but at if a little of the latter form is present to start the days reaction. The transition is accompanied by an increase in volume, and the product is a brittle substance which is readily powdered. The phenomenon was first observed in cold countries in the disintegration of organ pipes and other tin objects, and was called "tin disease." Grey tin is cubic, with the diamond lattice structure, while white tin is tetragonal with a ditetragonal-bipyramidal lattice. r-Tin belongs to the rhombic system. White tin is very malleable, and may be rolled into thin sheets called tinfoil, which has been used extensively for wrapping, but is now largely replaced by aluminum foil and
the ordinary white tin. The transition of or grey tin is slow at the transition temperais
by
It is very resistant to corrosion, whence its plastics. Tin does not, use in tinning iron and copper surfaces.
however, give the galvanic protection afforded by zinc 4), since tin is not a more powerful reducing agent (cf. VII than iron. Tin forms many useful alloys. (See Table VI
and also Copper and Bismuth.) The approximate percentage consumption of tin in America by various industries
is:
tinplate, 33; bronze, 27; solder, 21; and babbitt, 9. great saving in tin has been accomplished through the
replacement of the old dipping methods for the manufac-
344
REFERENCE

electrolytic deposition.
[Ch.
XV
ture of tinplate
by
used electrolyte
is
The most widely a bath containing phenylsulfonic acid

of lead
is
and
concerned largely with the reduction of the sulfide, and this may be brought about in several ways. (1) Part of the sulfide may be roasted to the oxide, PbO, or sulfate, PbSO4, and the oxidized ore
glue. 17. Lead.
The metallurgy
10
20
30
40
50
Per Cent Sn
60
70
80
90
IOC
FIG.
1.
Lead- tin temperature-composition curves.
heated with more of the sulfide
and
PbSO
PbS - 2Pb
2PbO 2S0
2.
PbS = 3Pb + SO 2 (2) The ore may

.
be roasted to the oxide and this reduced with carbon or carbon monoxide: PbO + CO = Pb + CO 2 (3) The sulfide may be reduced by heating with scrap iron: PbS + Fe = Pb + FeS. The iron may be added as such, or it may be produced in the furnace from a mixture of iron
7]
345
oxides and carbon. In the United States, the ore is gen5), and erally first concentrated by "flotation" (cf. VII
the smelting process is a combination of the three methods mixture of part roasted and part unoutlined above.
roasted ore with iron oxide and carbon

furnace.
is
heated in a blast
Copper present collects in the iron sulfide matte, while silver and gold dissolve in the molten lead. In the
tropositive impurities are generally
refinement of the crude blast furnace lead, the more elecremoved by melting the
TABLE
Britannia Babbitt
Antifriction
IV
ALLOYS OF TIN AND LEAD

Sn Sn Sn Sn Sn
Sn
90, 90,
75,
Sb 10 Sb 7, Cu 3 Sb 12.5, Cu
Hard
17.5
metal,
Pb
90,
Sb 10
Solder
50,
Pewter
85, 86,
Pb 50 Cu 6.8,
Zn
9,
Bi
6,
Sb
Ca 10 metal, Pb 82, Sb 15, Sn 3 White metal, Pb 75, Sb 14, Sn 10, Cu 1.7 Rose metal, Bi 50, Pb 27.1, Sn 22.9
Type
Battery plate, Pb 94, Sb 6
Frary metal, Pb 90,
Aluminum
solder
Al 5
metal and keeping

stirring.
it
molten for several hours with frequent
The
is
impurities,
off.
lead, especially if high in refined electrolytically, using as an elecbi.muth, trolyte a solution of lead fluosilicate. The crude lead serves as the anode, and a bag about the anode collects the
and are skimmed
when Some
oxidized, rise to the surface
now
recovered.
"mud" from which bismuth and the noble metals are The annual production of lead is about
is
1,500,000 tons, of which about one fourth the United States.
produced
in
Ordinary lead is very largely a mixture of the two isotopes, 208 and 206. Lead extracted from uranium ores is largely the lower isotope, and has a density of 11.27 as compared with 11.34 for ordinary lead. The crystal lattice of the metal is of the face centered type. The metal is so soft that it can be squirted, under pressure, into pipes and even into fine wire or rolled into thin sheets, but it lacks tensile strength. Lead may be hardened by the addition
346
REFERENCE
[Ch.
XV
of
antimony or the alkaline earth metals.
The most im-
portant industrial uses of lead are in the manufacture of storage batteries, preparation of white lead and other pig-
ments, manufacture of cable coverings, in plumbing, and acid works. Important alloys of lead are listed in Table IV. 18. Reactions of the Metals. The metals are powerful
in
reducing agents in the presence of an alkaline solution and Pure tin and lead do not fairly strong in acid solutions.
TABLE V
REACTIONS OF Ge, Sn, AND Pb
M 4- O - MO M + 2H+ = M^ H M 4- 2S = MS M 4- 2X = MX M + 2OH- - MO + H M = M++ -f 2e~

2
-f-
Lead forms PbO or Pb 3 O 4 Not with Ge. Slowly with Sn and Pb Lead forms only PbS With halogens, except PbI 4 Slowly with Sn and Pb. Ge forms
Ge0 Ge ca.
0.0,
Sn
0.14,
Pb
0.13 (values
3Ge
3Sn
-f-
4HN0 = 3GeO
8
in volts)
2 -f-
4NO
4-2H 2O
-f
4HNO = 3SnO
2
3
-f-
4NO
2
Forms
acid
slightly
soluble
metastannic
+ 2H O
3Pb
-f
-f-
8HNO - 3Pb(NO
2
3
3)
2NO 4- 4H Pb 4- 2CH C0 H 4- i0 = Pb(CH C0 2 4- H O - Pb(OH) 2 Pb 4- 2H 2 44- H 2O 2

2
2)
Also with other acids
Slowly at moderate temperatures
evolve hydrogen readily with acids due to high overvoltage effects (Append. I). Lead is quite resistant to the action of even moderately concentrated sulfuric acid, but is readily oxidized by oxygen in the presence of various weak organic
acids, e.g., acetic acid.
GERMANIUM COMPOUNDS
19.
Germanium
dioxide,
GeO 2
is
readily formed
by
The oxide is somewhat roasting the sulfide minerals. soluble in water with the formation of the acid. It is not
19]

in nitric or sulfuric acids,
347
more soluble
when heated with concentrated
dissolved or hydrohydrofluoric
is
but
chloric acids with the formation of volatile tetrahalides. The oxide is readily soluble in a mixture of oxalic acid and
ammonium oxalate; and also in triethanolamine. The halides are hydrolyzed in water with the precipitation of
the hydrated dioxide, except the fluoride, which forms a mixture of the dioxide and fluogermanic acid, H 2 GeF 6
.
The potassium
dioxide
is
3
.
but slightly soluble. soluble in alkalies forming germanates,

salt,
2
6,
GeF
is
The
e.g.,
Na GeO
2
Germanium
sulfuric acid
disulfide,
GeS 2 may be precipitated

,
in strong
by hydrogen
sulfide,
but yields a colloidal
It is soluble in alkali sulfide, suspension in dilute acid. thiogermanates. forming Germanium resembles silicon in the formation of an unstable hydride, GeH 4 and also traces of the heavier
,
compounds, Ge 2 H6 and GesH 8 when germanium compounds are reduced with aluminum in alkaline solution. The metal heated in a stream of hydrogen chloride forms This compound hygermanium chloroform, GeHCl 3 drolyzes to form germanous acid, which appears to resemble formic acid in structure GeHCl 3 + 2H 2 O = 3HC1
,
.
acid is soluble in alkalies, forming 4- HGeO(OH). germanites, and upon heating forms germanous oxide, GeO, which possesses basic properties in that it is soluble in acids. The monoxide sublimes at 710 C. and has been one of the principal difficulties in the electrolytes reduction of the element in molten electrolytes. Germanous halides and the sulfides may be prepared by igniting strongly the 4 compounds, e.g. GeI 4 = GeI 2 I2 The germanous
The
ion
is
readily
oxidized,
2H O
2
+ + Ge++ = GeO + 4H+

.
2e~, ca 0.3 volt.
Germanous
ion appears to be unstable
with respect to its own oxidation and reduction but halide complexes may be formed in solution by reduction of the 4 ion with hypophosphite. The compound (GeOOH) 2
348
REFERENCE

is
[Ch.
XV
analogous to oxalic acid ably unstable.
known.
Germanite ion
is
prob-
COMPOUNDS OF TIN
The stability of the two oxida20. Oxidation States. tion states of tin in respect to oxidizing and reducing agents
is
indicated
by the following
potentials:
VOLTS
Sn = Sn++ + 2e~ Sn++ = Sn+ +++ + 2e~ 3OH- -f Sn = HSnO 2 ~
+013
-0.13
HO
2
4-
3OH-
-f
HSnO 2 = Sn(OH) 6~ +
2
+HO+ ~
2e~
0.91
2er
0.96
It
-f-
follows from
Sn~H ++
~
these values that the

,
= 2Sn ++
equilibrium, Sn favors the reaction as written, that
is,
compounds may be reduced to stannous by the metal. The equilibrium is reversed in alkaline solu~ = Sn + Sn(OH) 6 tions: 2H 2 O + 2HSnO 2 21. Oxides and Hydroxides. The dioxide, SnO 2 is the principal tin ore. The crystal lattice is similar to rutile.
soluble stannic
. ,
When
fused with alkalies, the oxide forms stannates, e.g., Na2SnO 3 The alkali stannates are soluble in water, and upon the addition of acid to the solution precipitate
.
"a-stannic acid" or a-hydrous oxide. This acid or hydrous oxide is amphoteric, and readily dissolves in excess of either base or acid.
Another hydrous oxide, 0-oxide (also called metastannic is formed by the action of nitric acid upon tin or by the hydrolysis of stannic salts in hot solutions. This comacid)
pound is not soluble in excess of any acid, but is peptized by concentrated hydrochloric acid to form a sol which may be dissolved in dilute acid. The composition of the two
"acids" appears to be the same, the different behavior
being due to differences in physical state. X-ray diffraction patterns of both are identical with cassiterite. Sodium hydroxide dissolves the /3-oxide.
25]
349
22. Stannous oxide, SnO, may be prepared by heating stannous hydroxide or oxalate, or by heating the metal in a limited supply of oxygen. It burns when heated in air to form the dioxide. Hydrous hydrated stannous oxide,
probably
SnOH
O,
is
precipitated
by the addition
amphoteric,
of
dis-
alkalies to stannous solutions.
It is also
solving in alkali hydroxides, but not in ammonia or soluble carbonates. Solutions of stannites are powerful reducing
agents.
23.
and their 2 Sn 2 O7 and HSnO 4 Peroxystannic acids, are formed by the action of peroxides on stannic salts, solutions, or by the anodic oxidation of cold solutions of
,
alkali stannates.
24. Halides.
The anhydrous
stannic halides
may
be
prepared by the action of the halogens on the metal and aqueous solutions of the salts by dissolving stannic oxide in the hydrohalic acid. Complex halidostannates are
formed
in solution
and a number
of these soluble salts
be obtained upon crystallization, e.g., Stannic 2 SnF 6 chloride is important commercially as a mordanting agent. It crystallizes from an acid solution as SnCl 4 -5H 2 O although The ammonium the anhydrous compound is a liquid. is also used in dyeing under chlorostannate, (NH^SnCle, the name "pink salt." Stannous halides are readily prepared from the stannic by reduction with tin, or by dissolving the metal in the
.
may
halogen acid.
salt is
solutions are readily oxidized by Stannous chloride is also important as a mordant.
The
air.
The
very soluble in water, but forms the basic salt, Sn(OH)Cl, unless acid is present to prevent hydrolysis. 25. Sulfides. Stannous and stannic sulfides may be prepared by fusing the elements together, but the latter is
unstable at high temperatures: SnS 2
= SnS +
S.
Hydro-
gen sulfide precipitates brown stannous and yellow stannic sulfide from dilute acid solutions of stannous and stannic
salts respectively.
Both
sulfides are soluble in concen-
350
REFERENCE
[Ch.
XV
trated hydrochloric acid but stannic sulfide, being the more acid in nature, is the less soluble of the two. The disulfide
amphoteric and dissolves in excess of sulfide to form = SnS 3 The stannous sulthiostannates SnS 2 + S fide is not soluble in excess sulfide unless polysulfide is SnS present, in which case it is oxidized to thiostannate = SnSs The thiostannates arc not stable in 82
is
:
.
:
acid solution:
SnS 3
+ 2H 4 = H SnS = H
"
SnS 2
Stannic sulfide has long been used as a gilding pigment under the name of mosaic gold. The preparation is carried out by heating together a mixture of tin, sulfur, ammonium chloride, and mercury. The exact action of the two latter substances is uncertain, but they volatilize and leave the sulfide as brilliant yellow crystals. Small amounts of the hy26. Other Tin Compounds.
by the cathodic reduction of tin and by the action of acid upon tin-magnesium alloy. Both stannous and stannic carbonates are completely hydrolyzed to the hydroxides. Both of the nitrates and the sulfates are formed in solution by the action of the acids upon the hydroxides, but they are
dride,
4,
SnH
are formed
in dilute acid solution,
without the formation of basic salts. Slightly soluble stannous phosphate, Sn 5 H 2 (PO4)4-3H2O, may be precipitated from slightly acid stannous chloride by sodium acid phosphate, and a number of slightly soluble basic and double stannic phosphates are known.
difficult to crystallize
LEAD COMPOUNDS
The most important oxidation re27. Oxidation States. duction potentials for lead are given below:
VOLTS
Pb - Pb++ + 2e- PbSO 4 + 2e~ Pb + SO 4 Pb -f 30H- = HPb0 2 - + H 2 + 2ePb++ + 2H 2 - PbO 2 + 4H+ + 2c~ PbS0 4 + 2H 2 * Pb0 2 + 4H+ 4- SO 4
+ 0.126 + 0.355 + 0.54
PbO
+ 2OH- -
PbO 2
+H
~ + 2e~
2e~
- 1.456 - 1.685 - 0.25
29]

that lead
is is
351
It follows
and a strong reducing agent

the dioxide
acid solutions but
a fair reducing agent in acid solutions, in alkaline solutions, and that
an extremely powerful oxidizing agent in much weaker in alkaline solutions. 28. Oxides and Hydroxides. Lead forms the monoxide, PbO, and the dioxide, Pb02. Two additional oxides appear to be plumbous plumbate salts, the trioxide, Pb2O 3 being PbPbO 3 and red lead, Pb 3 O 4 being Pb 2 PbO 4 The existence of a so-called suboxide or its salts is extremely doubtful.
,
,
litharge, orange-yellow, is prepared by the metal in air; and around 550 C. the other oxides heating evolve oxygen to form the monoxide. The oxide is soluble in
The monoxide, or
acids and alkalies, forming respectively plumbous, Pb"^, and plumbite, HPbO 2~, ions, and the addition of alkalies
and
acid, respectively, to these solutions,
precipitates the
"hydroxide," or hydrous hydrated oxide, possibly PbO JH 2 O, which is soluble in excess of either reagent. The "hydroxide" is more basic than stannous "hydroxide" as is indicated by the formation of a carbonate. Litharge is used in glazing pottery and in making glass. A mixture with glycerine is sometimes used as a cement,
since
it
sets to a solid lead glyceride.
Red
lead or
minium
is
made by
carefully heating the
monoxide at temperatures below 500.
The composition
of the product varies with the temperature of roasting, a maximum of PbO 2 (33 per cent) is obtained at about
430.
When
treated with nitric acid,

3
it
is
2
Pb 3 O 4
is
+ 4HNO =
is
decomposed:
O.
2Pb(N0 3 ) 2
+ PbO + 2H
2
Red lead
Struc-
used in making
flint glass,
and as a red pigment.
often given a first coat of red lead paint as it serves very effectively to protect the iron from corrosion, due possibly to the iron becoming passive. 29. Lead dioxide may be prepared from red lead as
tural iron
indicated above, but it is most readily formed by the oxidation of lead monoxide or plumbites in dilute alkali soluCIO" = PbO 2 CJT. The oxide is also tions, e.g., PbO
352
REFERENCE
[Ch.
XV
readily prepared
lattice,
plumbous and
ion.
is
of solutions of dioxide has the rutile type of crystal a fair electrical conductor. It is only slightly
by the anodic oxidation
The
comparatively inert toward hydrogen and hydroxide ions. Concentrated alkalies do, however, dissolve the oxide forming plumbates, and soluble metaplumbates may be formed by fusing the oxide with alkalies. Many plumbates, both ortho and meta, of the 2 oxides have also been prepared. The more basic oxide is slowly soluble in dilute nitric acid, but the tetrapositive lead ion oxidizes water with the evolution of oxygen. Cold concentrated hydrochloric acid forms liquid tetrachloride, but at ordinary temperatures chlorine is For the use of the dioxide in the lead storage evolved.
soluble in water and
is
battery, see Paragraph 39.

30.
Lead Halides.
Lead
tetrafluoride
is
formed upon
heating the dioxide with potassium acid fluoride, although the product does not appear to be the pure compound.
The formation
of the tetrachloride is discussed in the preceding paragraph. In dilute acid, both halides are hydrolyzed to the dioxide; in the concentrated halogen acids,
and chloroplumbic acid, the fluoplumbic acid, 2 PbF 6 are formed. Alkali salts of both of these acids 2 PbCle,
,
have been prepared.

halides are but sparingly soluble in cold but the chloride and bromide are readily soluble in water, hot water, and the iodide partially soluble. The solubility
of the halide is decreased in dilute solutions containing the halogen ion but is increased in concentrated solutions,
The plumbous
doubtless with the formation of complex ions, such as

31. Nitrate.
The
nitrate,
Pb(NO 3 )
is
2,
but unless a slight excess of acid
readily soluble, present to prevent
is
hydrolysis, basic nitrates are precipitated. 32. Acetate. The acetate, Pb(C 2 3 2 ) 2 -3H 2 O, called sugar of lead, is one of the few soluble lead salts, and it
HQ
36]
353
appears to form a complex ion with excess acetate. Like the nitrate, the solution tends to form basic salts, but the basic compound, Pb(OH)C 2 H 3 O 2 is soluble. Both the acetate and nitrate are extremely poisonous. The dioxide is soluble in glacial acetic acid with the
,
formation of the tetra-acetate, but this compound is completely hydrolyzed in water. 33. Sulfate. The sulfate, PbSO 4 resembles the alkaline
,
earth sulfates in being slightly soluble in water. It is soluble in excess acetate (see above), and in excess alkali it dissolves to form plumbite. The basic sulfate, Pb 2 OSO 4
,
as the pigment 'sublimed white lead," is made by roasting lead sulfide with carbon. The product sublimes
'
known
and
is
cial
condensed to a pure white powder. The commerpigment usually contains excess of PbSC>4 and some
zinc oxide.
34.
Chromate.
soluble in water, but dissolves

of plumbite.
The chromate, PbCrO 4 is very slightly somewhat in acids with the

,
formation of dichromate, and in bases with the formation It is an important yellow pigment, chromeyellow. The stable yellow modification of lead chromate A red tetragonal modification may be stais monoclinic. bilized by the addition of lead molybdate. This pigment is
known
as
of the sulfide in the mineral has been discussed. The sulfide metallurgy is precipitated from dilute acid solutions by hydrogen sulfide, but is soluble in concentrated hydrochloric acid and in hot 2N nitric acid. It is not soluble in excess sulfide. The crystal has the sodium chloride type of lattice. It acts as a rectifier for oscillating electric currents. 36. Lead Carbonate. Normal lead carbonate, PbCO 3 may be prepared by the action of sodium bicarbonate solution upon lead chloride or sulfate. When soluble carbonates are added to a solution of lead ion, the basic carbonThis compound is exate, Pb3(OH) 2 (CO 3 )2, is formed.
36. Sulfide.
molybdenum orange. The occurrence

its
galena and
354
REFERENCE
[Ch.
XV
tremely important as the pigment white lead. The annual consumption in the United States is about 100,000 tons. It is prepared commercially by the action of air, carbon dioxide, and acetic acid upon the metal. A small amount of acetic acid serves to convert a large quantity of lead into the carbonate. The following reactions may represent the O 2 2HAc = 2Pb(OH)mechanism of the process: 2 Pb
Ac;
+ + + 2CO = Pb (OH) (CO )2 + 3PbAc + 2H O; and 2Pb + O + 2PbAc + 2H O = 4Pb(OH)Ac.

6Pb(OH)Ac
2
2 3 2
In the older forms of the process, perforated lead disks Tiers of were placed over pots containing acetic acid. with tan bark which decomposed these pots were stacked under bacterial action, liberating carbon dioxide and also providing heat. This process required about three months for completion, and more rapid methods are now being used to some extent, as for example, the churning of lead dust with acetic acid, air, and carbon dioxide. The covering power of white lead is excellent, but it has the disadvantage of darkening due to the formation of the sulfide, and its poisonous nature is also objectional. Lead Compounds. Lead orthophosphate, 37. Other Pb 3 (PO 4 ) 2 may be precipitated from dilute acid plumbous solutions by disodium phosphate. Many basic and double
,
Lead phosphates are also known. formed by fusing lead monoxide and
stituent of lead glass
silicate,
silica.
PbSiO 3
It is
is
a con-
and of certain glazes used on earthen-
ware.
38.
lator
Lead Storage Battery. The ordinary lead accumudepends upon the reversibility of the reaction: Pb = 2PbSO. + 2H 2 O. When fully PbO 2 + 4H+ + 2SO 4
charged, one electrode consists of a plate of spongy lead, the other electrode a plate impregnated with lead dioxide, and the electrolyte is sulfuric acid. The half reactions for
discharge
are:
4
Pb
+ SOr~ =
2<T
4H+
+ SO
PbSO 4 + 2e~ and PbO = PbS0 4 + 2H 0. Lead sulfate

2
2
thus forms on each plate upon discharge, and the concen-
39]
355
tration of sulfuric acid decreases.
The
density of the acid
under normal conditions
is
1.20 at 2.05 volts (charged)
and
1.05 at 1.91 volts (discharged). The cell is not completely reversible as is evident from the higher voltage required to
reverse
the
reaction
cell
and
2).
recharge the
(Fig.
The
final
rapid increase in
the charging voltage curve occurs when all the solid sulfate is used up and the
concentration of the lead ion diminishes.

39. Analytical.
AdvanFIG.
2.
tage
is
taken of the slight
Charge and discharge curves

C.
solubility of the sulfides of
for the lead storage battery at 15
the group in qualitative analysis. The reactions of these compounds with acids and bases have been discussed, and reference should be made to Appendix VI for the
treatment of tin and lead
The of the positive ions. first to mercurous and then to grey metallic mercury by stannous ion, is used as a confirmatory test for tin, and
the slight solubilities of the confirmation of lead.
the systematic separation reduction of mercuric chloride,

in
PbSO 4 and PbCrO 4
are used in
is determined quantitatively by precipitatas the disulfide and weighing as the dioxide. ing Tin is sometimes determined gravimetrically as the dioxide, but it is most readily determined by the volu-
Germanium
metric titration of stannous ion by iodine: Sn^ Is" = Sn 3I~. The reduction of any stannic salts prior to the titration is accomplished with aluminum foil in acid solution, or by nickel in hydrochloric acid. In gravimetric analyses, lead is often precipitated and weighed as the sulfate, PbSO 4 chromate, PbCrO 4 or molyb-
'
'
'
date, tion from
PbMoO
In the precipitation as the sulfate, separabarium is secured by dissolving out the lead in
4.
356
REFERENCE
[Ch.
XV
ammonium
tating.
acetate and dilute sulfuric acid, and reprecipiThe molybdate method has the advantage that
is
the barium salt
soluble.
often determined electrolytically by anodic preas the dioxide from a nitric acid solution, using cipitation a large platinum anode.
is
Lead
Chapter
XVI
SUBGROUP
1.
V.
VANADIUM, TANTALUM
NIOBIUM,
transition series
The elements
of
Subgroup
V occur in
resulting from the building up of the number of electrons in the outer shell of the kernel from eight to eighteen (Append. XVIII). Spectral data indicate that the normal
gaseous atoms have two electrons in the outer s orbital, so that three additional valence electrons must, in the normal atom, be located in lower d orbitals. However, all five valence electrons are removable, and all members of the group form compounds of the + 5 oxidation state. The elements are semi-noble, steel-like metals with high melting points. Vanadium forms compounds of all its possible positive oxidation states except + 1. Unlike the main Group V, the + 5 state becomes more stable with increasing atomic weight; and the pentoxide, which is amphoteric in the case of vanadium, becomes more inert to the action of both acids and bases. 2. Occurrence. Vanadium is estimated as present in rocks to the extent of 1.7 X 10~ 4 per cent, and igneous columbium and tantalum together as 3 X 10~ 5 per cent. The principal vanadium minerals are vanadinite, Pb 2 -
(VO4 )C1 (analogous

pucherite,
roscoelite,
2
BiVO4
to apatite); dechenite, [Pb, Zn](VO 3 )2; volborthite, [Cu, Ca] 3 (VO4 )2H 2 O; and
a vanadium mica containing V 2 C>3. Carnotite, K(UO )VO4 '3/2H 2 O, is also important as a source of uranium.
357
358
REFERENCE
[Ch.
XVI
Columbium
occur
(also called
niobium) and tantalum usually

minerals
.
together,
,
the
principal
are
columbite,
FeCb 2 O 6
and
tantalite,
FeTa 2 O 6
Other minerals are:
pyrochlor, calcium columbate, containing titanium, thorium and rare earths; yttrotantalite and fugersonite, complex oxide mixtures containing largely Ta 2 O 5 Cb2O 5 Yt 2 C>3,
,
,
and Er 2O 3
Vanadium is extracted from its ores by 3. Metallurgy. leaching out the ore with strong hydrochloric acid, and is precipitated from this solution as ammonium vanadate by
evaporation of the solution with excess of ammonium chloride. Ammonium vanadate, when roasted, yields the oxide. The preparation of the pure metal is a difficult operation. The reduction of the pentoxide with carbon in an electric furnace yields mostly carbide; and the reduction with aluminum gives a mixture of the metal and dioxide. The reduction of the dichloride with hydrogen is a satisfactory
method
of preparing the metal

is
on a small
scale.
Very prepared commercially, however, as the steel industry, which is the principal consumer, employs ferro vanadium. This is manufactured by the reduction of the mixed oxides with carbon in an eleclittle
of the pure metal
tric furnace.
small
amount
of
vanadium
is
making metavanadate
facture of sulfuric acid.
for use as a catalyst in the
consumed in manu-
separation of pure columbium and tantalum oxides from their ores is largely an analytical problem (Par. 17). The metals may be prepared by the reduction of the complex alkali fluorides with sodium, or the oxide with metallic calcium or aluminum. Tantalum may be electroplated from the fused complex potassium fluoride, but the electro-
The
not very satisfactory and the generally prepared by heating a mixture of the oxide and carbide at 1600 C. 4. The Metals. The more important physical properties are given in Table I. The metals are grey or silver white
deposition of niobium
is
metal
is
5]
SUBGROUP
V.
VANADIUM, NIOBIUM, TANTALUM

TABLE
359
in color,
they
may
7),
and do not tarnish readily. Though very hard, be rolled or hammered, and drawn into wire.
is
Vanadium
used extensively in the steel industry
(cf.
add tensile strength to steel. Columbium in the form of ferrocolumbium is employed in the manufacture of chromium steels to render them more weldable. Tantalum was formerly employed in electric light filaments, but hasêen replaced by tungsten. The metal,
to
in spite of its electropositive character, is extremely resistant to chemical action at ordinary temperatures and
XIX
being employed as pipes, kettles, and containers in many chemical manufacturing processes, displacing platinum, and other expensive metals. Due to the passive nature of tantalum, it exhibits, to a high degree, an electrolytic valve action (see Aluminum, VI 17) and is employed in cells to act as current rectifiers. Tantalum absorbs gases readily at high temperatures; and becomes hard and brittle. For this reason, the metal must be worked cold or in a
is
vacuum.
Because of
its
hardness tantalum carbide
is
employed as a constituent of hard cutting-tool mixtures. The metals are attacked 5. Reactions of the Metals.
by oxygen only when heated. Vanadium and niobium are dissolved by nitric acid and other powerful oxidizing
360
REFERENCE
[Ch.
XVI
agents (Par. 6) but tantalum is attacked readily only by a mixture of nitric and hydrofluoric acids. The general reactions of the group are summarized in Table II.
;
TABLE
4M + 5O = 2M O 2M 4- 5X = 2MX
2 2
6
II
REACTIONS OF VANADIUM, NIOBIUM, AND TANTALUM

2
6
Heated. Heated.
Br.
also forms
VO
Ta and Nb with
and
F, Cl,
and
3 |H 2 2Na 2 O Fused. Ta and Nb form Na 8 M 6Oi 9 3M -f- 15HF -f- 5HNO 3 = 3H 2 MOF& + 5NO + 7H 2O Also other complex fluo-acids 2V + Si = V 2 Si High temperature 2Cb 4- H 2 = 2CbH
M + C = MC M + 2S = MS M + 5NaOH = NaMO +
2
6M + 5N 2 = 2M N
3
form only VC1 4 and Heated. V forms VN High temperature Heated. V forms V 2 S 5 also
Nb
VBr 3
VANADIUM COMPOUNDS
Vanadium forms compounds posthe oxidation states 2, 3, 4, and 5. The two lower sessing valences are basic; but the two higfher are amphoteric
6.
Oxidation States.
though
in the
aqueous
solutions, the positive ions exist

.
+ only as vanadyl, VO++, and pervanadyl, V(OH) 4 Oxidation-reduction potentials involving the states are summarized below:
various
VOLTS
V . V++ + 2e~ V 4 + V+++ + e~ V++*- + H O - VO++ + 2H+ + e~ VO++ + 3H O - V(OH) + + 2H+ +

2
2
4
+1.5 +0.2
tr
0.314
1.00
From
these values,
it follov/s
i.e.
centrated hydrogen ion,
that vanadic acid in conV(OH) 4 + is a moderately
powerful oxidizing agent; but the hydrogen ion is involved to such a high power that the potential decreases markedly in dilute acid, so that vanadate in neutral solution is not easily reduced. As the potentials indicated, the reduction products depend upon the strength of the reducing agent
f
8]
SUBGROUP
V.

1
361
Fe ++ gives VO" Vanadous ion, V"*"*",

e.g.
"1
",
is
Sn +H gives V+ ++ and Zn gives a strong reducing agent, and vanadic

~
,
ion
is
fairly strong.
The metal
is
oxidized
oxidizing agents in acid solution to the
by moderate 4 state and by
powerful agents to vanadate. The monoxide, VO, is prepared by 7. The + 2 State. the reduction of vanadyl chloride, VOC1 2 by carbon, zinc, or hydrogen at red heat. The oxide is semi-metallic in appearance and was considered by Berzelius to be the metal. The hydroxide, V(OH) 2 is but slightly soluble. Its salts in solution have a deep violet color. The sulfate, VSO4 is prepared in solution by the reduction of sulfuric acid solutions of vanadates by zinc, or by cathodic reduction in an atmosphere of carbon dioxide. The solid hydrate, VSO 4 '7H 2 O, may be obtained upon evaporation, and double sulfates are formed with the alkali sulfates, The sulfate solution absorbs nitric oxide, 2 V(SO 4 ) 2 -6H 2 O. ~ similar to ferrous ion, and the complex cyanide, V(CN) 6 4 is similar to ferrocyanide in the solubilities of its salts. The anhydrous chloride and the sulfide are prepared, re= VC1 2 + 2HC1, 2 spectively, by the reactions: VC1 4 + and V 2 S 3 + H 2 = 2VS + H 2 S. The latter is not soluble
,
, ,
in dilute
hydrogen ion or
in sulfide ion.
8. The + 3 State. In formulas and solubilities, the vanadic compounds resemble ferric, but unlike the latter, they are readily oxidized. The salts in solution are green; and the green hydroxide, V(OH) 3 is precipitated from
,
by ammonia or alkali hydroxides. The It is rapidly oxidized by air to form the dioxide. V 2 O 3 may be obtained by reducing the pentsesquioxide, oxide with hydrogen or carbon, and the product is insoluble in most acids. Solutions of the halides may be prepared by dissolving the hydroxide in the halogen acid. The anhydrous compounds may be prepared by reactions 2 and V 2 O 8 analogous to the following: 2VC1 4 = 2VC1 3 + + 3Br 2 + C = 2VBr a + SCO. The oxychloride, VOC1, is
solutions of its salts
,
362
REFERENCE
[Ch.
XVI
but slightly soluble. Reduction of sulfuric acid solutions of the pentoxide gives vanadic sulfate, V 2 (SO 4 ) 3 in solution this salt readily forms alums. The oxide reacts when heated with ammonia, and with hydrogen sulfide, to give the nitride, VN, and the sulfide, V 2 S 3 respectively. The
,
latter is soluble in dilute acids.
Vanadic ion forms many complex and double salts, the most important being double fluorides, as (NH 4 ) 3VF 6 or (NH 4 )2VF5 double oxalates as, K 3V(C 2 O4 ) 3 -3H 2 O; complex cyanides as K 3V(CN) 6 and sulfocyanides, K 3 V(CNS) 6
, ;
+ 4 State. The dioxide, VO 2 may be obtained by partial reduction of the pentoxide; the hydrous oxide, is precipitated by the addition of sodium carbonate to vanadyl salts in solution. The hydrous oxide is oxidized in air. It is soluble in the alkali hydroxide and in ammonia, These compounds 2 V4 O 9 -7H 2 O. forming vanadites, e.g. in solution have a deep black color, are not readily oxidized, and form slightly soluble vanadites with the heavy metals.
9.
The
dioxide dissolves in acid to form the blue vanadyl ion, VO^" ", and many salts of this ion are known, e.g., VOC1 2 VOSO 4 The anhydrous chloride is formed by the
1
,
The
reactions:
V +
2C1 2
It is
= VC1
4,
and
VOC1 3
1/2C1 2
+C
a heavy liquid with an extremely low melting point. The water solutions hydrolyze to vanadyl chloride. The addition of sulfide to an acid vanadyl
solution precipitates the sulfide, VS 2 which is soluble in excess sulfide to form thiovanadites. 10. The 5 State. The oxide, 2 O 5 may be prepared
,
= VC1 4 + CO.
by roasting ammonium metavanadate, NH 4 VO 3 or by the hydrolysis of pervanadyl chloride, VOC1 3 It is some;
what
soluble in water to give a slightly acid solution, but with excess of hydrogen ion the acid forms pervanadyl + VO 2 Metavanadic acid, HVO 3 4 ion,
V(OH)
(or
+).
may
be precipitated as golden yellow solid by the action of sulfurous acid upon copper vanadate. The acid is sometimes employed as gold bronze. Pyrovanadic acid, H 4V 2 O 7
,
fO]
SUBGROUP
V.
363
is
precipitated
by the
addition of nitric acid to vanadate
solutions.
The
addition of alkali to vanadic acid results in the
formation of complicated poly-anions. Sodium salts of the meta-, ortho-, pyro-, and hexa-vanadic
acids are
known:
NaVO Na VO Na V O Na H V
3,
3
4,
7,
On.
The metavanadates
sodium, potassium, ammonium, barium, and lead are but slightly soluble in cold water; but salts of other positive ions are soluble, and the color
of
generally yellow. The alkali pyrovanadates are soluble. In solution orthovanadate is readily hydrolyzed: 2VO 4 = 2O7 2O + 2OH~. At high temperatures, the ortho salts are stable, however, and constitute many of
is
+H
the
is
vanadium
minerals.
The most important compound

3,
probably ammonium metavanadate, N,H 4 VO which is precipitated by excess ammonium chloride from meta- and
In recent years large quantities pyrovanadate solutions. have been used in the preparation of the vanadium catalysts for the manufacture of sulfuric acid. The alkali metavanadates are readily converted to peroxyvanadates, MVO 4 by hydrogen peroxide; and peroxyvanadic acid, HVO 4 is formed when the pentoxide is added
of the salt
, ,
to a solution of hydrogen peroxide in sulfuric acid. solution has a deep red color.
The
Of the pervanadyl compounds, the most important is probably the pervanadyl sulfate, (VO) 2 (SO 4 ) 3 This may be obtained as a red-brown solid upon evaporating the acid solution, and basic salts as, VO(OH)SO 4 are also formed.
.
,
With concentrated hydrochloric
acid, chlorine is evolved
and the dioxide formed. However, the pervanadyl chloride may be made by the action of chlorine upon VO or V 2O 3 or upon a heated mixture of the pentoxide and carbon. The chloride is a heavy low melting liquid with a lemonyellow color. It fumes in moist air and is hydrolyzed by water to vanadic acid. Complex oxyfluovanadates, as K 2 VOF6 and K 2VO 2 F 3 are precipitated by the addition
,
,
364
REFERENCE

to the
[Ch.
XVI
of potassium
tions.
fluoride
pervanadyl fluoride solu-
Ammonium
VS
sulfide acts
.
upon vanadate solutions to form

acid to this solution
2
5,
thiovanadate, VS4 precipitates the sulfide,
The addition of
VS
or possibly a mixture of
S6
and
2.
COLUMBIUM COMPOUNDS
Oxidation States. The compounds of lower states less stable than in the case of vanadium. The 5 compounds which may be obtained in acid soluonly + tion are the complex fluoride and chloride, and these solutions may be reduced quantitatively by zinc in the cold to a blue solution of the + 3 columbium but, if the solution is heated, a precipitate of mixed oxides, possibly CbC>2 and Cb 2 O3, is formed. The + 3 compounds in solution
11.
are
much
by oxygen. The oxychloride, be reduced by sodium to the monoxide, may CbO, which dissolves in acid with the liberation of hydrogen. The pentoxide may be reduced by magnesium to the dioxide, CbO 2 which is not attacked by acids, but burns
are oxidized very rapidly
CbOQ
3,
in air
when
heated.
Due
to the passivity of the metal
and the inertness
of
the oxide, very little is known about the true oxidationreduction potentials of columbium, and the following values are calculated from thermal data.
VOLTS
2Cb
Cb
12.
+ SH O - Cb + - Cb ++ + + 3e~
2
2
10H+
10<r
ca.
0.62
1.1
Pentoxide and Columbates. The pentoxide, Cb 2 O 6 may be prepared by decomposing the potassium oxyfluoride with sulfuric acid. With concentrated acid the oxide dissolves with the formation of some complex ion, possibly Cb(SO 4 )3~- The pentachloride hydrolyzes in water to give the meta-acid, HCbOs. The oxide and acid when fused
,
12]
SUBGROUP
V.
365
with alkalies or alkali carbonates yield complex columbates. Potassium hexacolumbate, K 8 Cb 6 Oi 9 -16H 2 O, is readily sol* uble in water, and with excess of alkali forms a number of
other
salts,
such as
KtQ^CVUHUO.
,
Peroxycolumbates are formed by the action of peroxides upon columbates; and the peroxy-acid, HCbO 4 is obtained as a yellow solid when columbic acid is warmed with hydrogen peroxide.
Halogen Compounds.
Columbic acid
is
soluble in hy-
drofluoric acid; the addition of potassium fluoride to the solution yields fluocolumbate, and in less concen2 CbF 7
trated
2
acid
5.
double
salts
of
the
oxyfluoride,
such
as
K CbOF
The
pentachloride, CbCl 5 is formed by passing chlorine a heated mixture of the oxide and carbon; or sulfur over chloride, S 2 C1 2 over the oxide. The pentachloride is soluble in hydrochloric acid. The oxychloride is a volatile solid, and like the chloride, is completely hydrolyzed in water. Corresponding compounds of fluorine and bromine have also been prepared, which have rather similar properties. At red heat, the pentachloride decomposes into the This anhydrous chloride is not decomtrichloride, CbCl 3 posed by water, but is readily oxidized with nitric acid,
,
and when heated reacts with carbon dioxide: CbCls + CC>2 = CbOCl 3 + CO. Other Compounds. The m<ptal heated in nitrogen at 1200 forms the nitride, Cb 3 N 5 Mixed oxide-nitride compounds result from the action of ammonia upon the oxide at red heat, but the nitride NbN is formed by the action of ammonia upon the metal at red heat. The metal unites with hydrogen when heated to form the hydride, NbH, which is not attacked by acids, but
.
readily burns in air.

fide
The
oxide
is
not converted into sul,
sulfide, but oxysulfides, e.g., Nb 2 O 2 S 3 form when the oxide is heated in an atmosphere of carbon dioxide and carbon disulfide.
by ammonium
3,
NbOS
366
REFERENCE
[Ch.
XVf
TANTALUM COMPOUNDS
13. Although there is very little experimental work on the oxidation-reduction potentials of tantalum, the value for the heat of formation of the pentoxide, 484,500 cal., leads to the following approximate potential:
2Ta
+ 5H O
2
- Ta 2O5
10H+
10<r
0.71 volt
No compounds
aqueous solution.
rapidly.
of lower oxidation states are stable in
The -f 2 chloride has been prepared at but the water solution evolves hydrogen high temperatures,
14. Pentoxide and Tantalates. The pentoxide, Ta 2 O 5 formed when the metal burns in air. It is left as a residue when tantalates are fused with potassium acid sulfate, and the product extracted with hydrochloric acid. The oxide is very inert, but when fused with alkali hydroxides forms hexatantalates, e.g. Na 8Ta 6 Oi9*25H 2 O. These compounds are soluble in water. When ignited with ammonium chloride, metatantalates, e.g. NaTaO 3 are formed these are not
,
is
soluble.
The meta-acid,
is
HTaO
3,
is
precipitated
when the
pentachloride
added to water.
solution of potassium hexatantalate gives with per-
which may be oxide a peroxytantalate, 3 TaO 8 'l/2H 2 O, precipitated from the solution by the addition of alcohol.
is decomposed by sulfuric acid to give the which is fairly stable. 4 acid, The pentoxide reduced with magnesium yields a monoxide, TaO, which is not soluble in acids, and burns in
The compound
HTaO
air to the pentoxide.
ignited pentoxide is not soluble in any acid, but the hydrated oxide dissolves in hydrofluoric acid, and either
The
dissolves slightly, or
16.
is peptized by other acids. with the Halogens. The pentafluoride, Compounds chloride, and bromide, form when the metal is heated in the corresponding halogen. Alkali fluotantalates, e.g.
17]
SUBGROUP
7,
V.

by
367
K TaF
2
are obtained
dissolving the hydrated pentoxide

alkali
fluoride.
in hydrofluoric acid,
and adding
These
compounds are easily soluble in hot water, but much less soluble in cold. When the solution of the potassium salts
is boiled,
an oxyfluoride, KtTatQ&Fu,
precipitates.
The pentachloride and bromide are most readily prepared by heating a mixture of the oxide and carbon in a stream of chlorine. These compounds are readily volatile around 150, and are completely hydrolyzed by water. 16. Other Compounds. The sulfide, TaS 2 is said to be formed by the action of hydrogen and carbon disulfide upon the heated oxide. It is not soluble in hydrogen ion. When the chloride is heated in ammonia at not too high a temperature, a bright red nitride, Ta 3 N 6 is formed. At higher temperatures, the compound TaN is produced. The pentanitride is also formed when the metal is heated in
, ,
nitrogen at 1000
C.
is
carbide, TaC, forms when the oxide carbon at high temperatures.
The
reduced with
17. Analytical.
The
slight solubility of the oxides of
vanadium, columbium, and tantalum in dilute hydrogen ion, and in oxidizing agents, and their ready solubility in hydrofluoric acid, places them analytically in a group con-
Sb O 5 SnO WO MoO TeO 2 V2 O4 TiO Ta O 6 Cb Os, and Bi 2 Oa, together with phosphates of Sn, Ti, and Zn When these oxides are dissolved in hydrofluoric acid and treated with ammonium sulfide, a separation is obtained, giving in the filtrate, the thio-salts of Sb, Sn, W, Mo, Te, V, and a residue of TiO 2 Ta 2 O Cb 2 O 6 Bi O 3 and Ti
sisting of
2 2
,
2,
3,
3,
2,
5,
and Zr phosphate or vanadate. The presence

in the thio-salt solution is recognized color of (NH 4 ) 3VS4
.
of
vanadium
violet-red
by the
is
When
sodium
the
TiO 2 Ta 2 O 5
,
etc. residue
above
boiled with
salieylate solution, the titanium and vanadium are extracted. The residue is fused with 2 COs; and KgTaaOig and KsCbsOis are obtained in solution by extracting with
368
REFERENCE
[Ch.
XV
cold water. The tantalum is separated from the niobium by the smaller solubility of the potassium oxyfluotantalate,
and the niobium recognized by reduction to NbCl 3 blue, with zinc, and the reaction of this solution with mercuric chloride to give mercurous chloride. The fractional crystal,
lization of the
be employed.
K TaF
2
7,
5;
complex fluorides with excess HF may also The solubility data in grams per liter are: K 2 TiF 6 -H 2 O, 12; and K 2 NbOF 5 -H 2 O, 77.
In gravimetric determinations, these elements are usually separated and weighed as the pentoxides. Vanadium and niobium are determined volumetrically by reduction to 3 niobium, and titration with vanadyl and to the
permanganate.
The variation in the 18. Summary of Potential Values. oxidation reduction potentials for the members of the group are indicated in the following potential diagrams.
(1.5)
0.25
0.36
1.0
-V(OH) 4 +
Nb O 5
2
0.71
Ta
Ta 2O5
Chapter XVII
SUBGROUP VI. CHROMIUM, MOLYBDENUM, TUNGSTEN (WOLFRAM)

1.
The elements
of
Subgroup VI have 6 as the maximum
positive oxidation state and in this state show many properties common to each other, as well as to sulfur in the In addition, the elements of the group have a sulfates.
variety of lower oxidation states, in which they do not resemble each other as much as they do the elements of higher and lower atomic numbers; especially is this true of chro-
mium, whose lower states are similar to the corresponding ones of vanadium and manganese. This fact is to be correlated with the position of the elements in transition series in which an eight electron shell is being converted to an
eighteen electron shell (Append. XVIII). One of the most striking properties of the + 6 compounds is the tendency to form poly-acids. This tendency reaches a maximum in molybdenum, which forms acids containing many molecules
The acidic nature of the oxides decreases with increasing size of the ions. The metals have very high melting points, that of tungsten being higher than that of any other metal. They are also very tough, and advantage is taken of this in forming many important alloys with iron. Uranium was formerly included in Subgroup VI, but the evidence is now definite that it contains electrons in the 5f shell and its chemistry is discussed with the element of the Actinide series. Tungsten is also known as wolfram.
of the trioxide.
369
370
REFERENCE
[Ch.
XVII
Occurrence. The metals do not occur free in nature. is the most abundant of the group, and is present to the average extent of about 0.037 per cent in igneous rocks, usually as Cr 2 O 3 replacing Al 2 Oa in alumi2.
Chromium
nates.
The estimated
10~"
6
,
percentages of the others are molyb:
denum
and tungsten
is
,
10~~
5
.
The most important

.
chromite, Fe(Cr 2 O 4 ), or FeO-Cr 2 O 3 Lead PbCrO 4 and other chromates of the heavy chromate, metals also occur. The major chromite-producing countries
chromium
ore
Caledonia, Rhodesia, South Africa, Russia, and Cuba. The domestic deposits are very limited. Turkey Molybdenum is most frequently found as the sulfide, molybdenite, MoS 2 which resembles graphite in appearance. It also occurs as molybdates, especially PbMoO 4 and Fe 2 (MoO 4 )3*7.5H2O. Extensive deposits of molybdenite
are:
,
New
occur in Colorado. It is estimated that the known reserves of "proved ore" in this state are around one million tons
of
molybdenum.
wolframite, an iso4 morphous ferrous-manganous tungstate, [Fe, Mn] Other tungstates, as CaWO 4 PbWO 4 and 4 and the China trioxide, WOa, or wolfram ocher, are also found.
ore
is
The most important tungsten

,
WO
CuWO
and Burma have been the leading producers Domestic production is largely from Nevada.
of tungsten.
METALS AND METALLURGY

3.
Chromium.
is
The
mium
utilized in
chrome
greater portion of metallic chrosteel, and for this use ferro-
chrome
is prepared by the direct reduction of chromite by 2Cr carbon FeCr 2 O 4 4- 4C = Fe 4CO. For the prepa:
chromium compounds, the ore is usually fused with sodium carbonate in air: 4FeCr 2 O 4 + 8Na 2 CO 3 + 7O 2
ration of
= 2Fe 2 O3 + 8Na2 CrO 4 + 8CO 2 the sodium chromate is then extracted with water. The pure metal is conveniently
;
prepared by reducing chromic oxide with aluminum (Gold-
4]
SUBGROUP
VI.
CHROMIUM, MOLYBDENUM,
ETC.
371
The
schmidt reaction), or with carbon in an electric furnace. electrolytic deposition of chromium on iron or copper has recently assumed importance. The electrolyte used is an acid chromic chromate solution containing sulfate, phosphate, borate, or other acid radicals. Chromium is similar to platinum in luster, and this together with its high resistance to corrosion, has resulted in
the use of the electroplated metal on motor cars and miscellaneous domestic appliances. Chrome steel (0.5 to 1.0 percent Cr, 0.75 percent Si, and
0.5-1.25 per cent Mn) is very hard and tough. Stainless steel (14 per cent Cr) is used in the manufacture of cutlery, valves, turbine blades, etc. Nichrome (60 per cent Ni, 15
per cent Cr, and 25 per cent Fe)

in electrical heaters.
is
used as resistance wire
or
Chromium, with cobalt and tungsten, forms an alloy known as stellite, suitable molybdenum,
for high-speed tools (cf.

It is
XIX
19).
estimated that 50 per cent of the American consumption of chromate is for metallurgical industries, 40 per cent for the manufacture of refractory chrome-brick for furnace lining, and 10 per cent for the chemical industries.
The sulfide ore is now generally the oxide and converted into calcium molybdate roasted to by the addition of lime. This product is then used directly
4.
Molybdenum.
in the production of alloy steels or
made
into ferromolyb-
denum by reduction with carbon in an electric furnace. The pure metal may be prepared by reduction of the oxide with aluminum or hydrogen, and also by the electrolytic reduction of molybdic acid. Molybdenum is silver white in
color, tough,
and
ductile.
It is
added to low carbon

1
steel
as a toughener; the addition of
per cent of
molybdenum
doubles the strength of low carbon steels at temperatures above 475 C. Such steels are used, for example, in superheated steam plants. The addition of molybdenum to chrome (stainless) steel increases the resistance to chemical
372
REFERENCE
[Ch.
XVII
action.
High molybdenum
steels are finding increasing
use as high-speed tools.
Tungsten. Tungsten is generally obtained from wolframite ores by fusion with sodium carbonate, to convert to sodium tungstate, which is then extracted with water, and the solution digested with hydrochloric acid to precipitate tungstic acid. The acid is reduced by heating strongly with carbon, but the product is a powder, as the temperature is far below the melting point of the metal. Rods of the metal are formed by sintering the particles together by passing a
6.
strong electric current through the compressed powder. Tungsten has become one of the most important industrial
metals.
ment
electric
In 1950 a billion and a quarter of tungsten lamps were sold in the United States,
fila-
In
TABLE
order to draw the metal into wire, it is necessary to subject the rod to severe working at a low temperature to break up the large crystals which form when the metal is heated and render it brittle. The tensile strength of the drawn wire
exceeds that of any other metallic substance. The metal is also used as contact joints for making and breaking electrical circuits, for internal
combustion engine valves, X-ray
6]
SUBGROUP
VI.
ETC.
373
apparatus and utensils. The metal may be electroplated from solutions of sodium tungstate, but the best coatings are secured by deposition with nickel (or other rnetals).
The
nickel-tungsten (35-50 per cent W) alloy surfaces have remarkable resistance to chemical action.
Ferro-tungsten can be prepared by the reduction of the purer forms of iron tungstate ore with carbon. It is employed in the manufacture of "high-speed" steels and cobalt 19). alloys such as stellite (cf. XIX In recent years, tungsten carbide, WC, has assumed great importance as a cutting material. Tungsten carbide
extremely hard but quite brittle. To overcome the it is imbedded in a matrix of some tough metal, cobalt. These cemented carbides are the hardest frequently metals so far produced.
is
brittleness
TABLE
II
REACTION PRODUCTS OF THE ELEMENTS
6.
Reactions of the Metals.
The
reactions of the metals
reagents are so varied in nature as to render them difficult to summarize in the form of general group reactions; however, the principal reaction products have
with
common
374
REFERENCE
[Ch.
XVIl
been summarized in Table II. The lighter members of the group exhibit to a high degree the property of passivity, and their reactions with powerful oxidizing agents are thus often
extremely slow.
COMPOUNDS OF CHROMIUM
which
Oxidation States. Chromium forms compounds in it has the oxidation numbers + 2 (chromous), + 3 (chromic), and + 6 (chromate). The + 2 state is basic, the + 3 state is amphoteric, and the + 6 state is acidic. The potential relations between the states are summarized in the
7.
following half reactions
VOLTS
Cr Cr++ + 2er .................................... Cr++ = Cr +++ + er ................................ 20+++ + 7H 2O = CrjCY + 14H+ + 6c" ..............
It is
+ 0.86 + 0.41
1.36
evident from these values that the chromate in acid The equilibrium, is a powerful oxidizing agent. Cr + 2Cr ++ + = 3Cr++ favors the formation of chromous ion, but the latter is such a powerful reducing agent that its
solution
,
solutions are oxidized even
by very weak oxidizing agents
to chromic ion.
Chromous Compounds. Chromous compounds are somewhat similar to ferrous. Chromous hydroxide, Cr(OH) 2
8.
,
is
a slightly soluble, brownish yellow substance, which is oxidized readily in air and when heated liberates hydrogen
2 2 2
.
Solutions 2Cr(OH) 2 = Cr O 3 + H O + H ion are blue, and may be prepared by the
of
chromous
reduction of
chromic solutions by the metal or by zinc (see above). The chloride and sulfate are soluble. The former may be prepared as an anhydrous salt, by heating the metal in hydrogen chloride. The sutfide, CrS, and carbonate, CrCO 3 are but slightly soluble, and the acetate, Cr(C 2 H 3 O 2 )2, but
,
moderately
9.
so.
Chromic Compounds.
The
oxide,
is
stable of the
chromium
oxides,
and
Cr 2 O 3 is the most formed by heating the

,
10]
SUBGROUP
VI.
CHROMIUM, MOLYBDENUM, ETC
375
metal or other oxides in air. Due to its fine green color it is used as a pigment, chrome oxide green. This is generally prepared by igniting sodium dichromate with sulfur or am-
Na Cr O + S = Cr O + Na SO and Na Cr O + 2NH Cl = Cr O + 2NaCl + N + 4H O. A hyThe oxide is isomorphous with corundum, Al O drated oxide, Cr O 3 'H O, may be formed by hydrolysis
monium
2 2
chloride:
3.
no evidence for the existence of Cr(OH) 3 The so-called "hydroxide" which is precipitated from chromic solution, may best be described as a hydrous
under pressure, but there
.
is
oxide.
In
its
nH
is
O, resembles
amphoteric properties the hydrous oxide, Cr 2 O 3 aluminum hydroxide, and like the latter
precipitated by ammonium hydroxide, and by solutions of alkali sulfides and carbonates. Excess of alkali hydroxide
dissolves the precipitate with the formation of chromites, but the hydroxide or hydrated oxide is precipitated upon
boiling. Chromites are readily formed by fusing the oxide with metal oxides, and such compounds constitute the common chromium minerals, the most important being ferrous Chromite is used extensively as a rechromite, FeCr 2 O 4 in lining open-hearth furnaces used in fractory, especially the manufacture of steel. 10. Chromic ion forms numerous coordination complexes, especially with ammonia, water, halides, cyanide, and thio.
cyanate. A number of these are tabulated below. The coordination number of chromium is six. In solution these compounds dissociate into the complex ion and the ions
placed outside the bracket.
[Cr(NH 3 ) 6 ]Cl 3 [Cr(NH 3 ) 6 Cl]Cl 2

[Cr(H 2 0) 6 ]Cl 3 [Cr(H 2 0) 4 Cl 2 ]Cl
[Cr(NH 3 ) 6 ](CNS) 3 [Cr(NH 3 ) 3 (CNS) 3 [Cr(CNS) 6 ]K 3 [Cr(CN) 6 ]K 3

]
"
l
[Cr(NH 3 ) 5 (H 2 O)]Cl 8 [Cr(NH 3 ) 5 NO 2 ]Cl 2

[Cr4 O(SO 4 )4]SO 4
[Cr(OH)(NH 3 ) 6 ]Br2
The two water-chloride complexes are of especial interest. The complex ion, [Cr(H 2 O) 6 4" + has a violet color, and is
]
,
376
REFERENCE
[Ch.
XVII
present largely in dilute chromic ion solutions, while the complex, [Cr(H 2 O) 4 Cl 2 ]+, is green and forms in more conThe centrated solutions in presence of excess chloride. rates of transition are slow, however, and the two ions may
chloride
be obtained in the same solution. Only one third of the may be precipitated from the green solution by
11. Chromic sulfate, Cr 2 (SO4 ) 3 '18H 2 O, may be precipitated by the addition of alcohol to a solution made by dissolving the oxide in sulfuric acid. This solution is violet,
~
,
silver ion.
~ H + vide supra, but upon heating a probably Cr(H 2 O) 6 green sulfate solution is formed, which does not form a precipitate upon the addition of alcohol, and in which only one third of the sulfate is ionized. Upon standing, the green solution reverts to the blue. Chromic sulfate readily forms alums, e.g., KCr(SO 4 ) 2 -12H 2 O. Chromic phosphate, CrPO 4 -6H 2 O, precipitates when sodium hydrogen phosphate is added to a chromic solution. Several other hydrates are formed by carrying out the pre-
cipitation at higher temperatures.

12. Chromic Acid and Derivatives. Chromic anhydride, or chromium trioxide, separates as a mass of scarlet needles when a cold concentrated solution of potassium dichromate is treated with concentrated sulfuric acid. It melts without
decomposition, but loses oxygen around 250 to form the oxide, Cr 2 O 3 'CrO 3 or CrO 2 and at higher temperatures,
, ,
in water, forming chromic and dichromic acids, H 2 CrO 4 and H 2 Cr 2 O 7 The former may be crystallized from warm concentrated solutions. A solution of chromic acid, formed by adding sulfuric acid to sodium dichromate, is frequently used in the laborais
.
Cr 2C>3.
The
trioxide
very soluble
tory as "cleaning solution." Like the other members of the sixth periodic group, chromate forms complexes containing varying amounts of the trioxide; and the potassium salts, 2 CrO 4 2 Cr 2 O 7 2 Cr 3 Oio, and 2 Cr4 Ois are known. However, only the
12]
SUBGROUP
VI.
377
solution,
two are important, the chromate existing in alkaline and the dichromate in acid solutions. The equilibrium between the two ions is represented by the equation 2CrO 4 + 2H+ = Cr 2 O 7 + H 2O, = 4.2 X 10 14 The mechanism of the equilibrium involves the two equilibria: = 3.2 X 10~7 and 2HCrOr HCrOr = CrO4 + H+, = H 2 O + Cr 2 7 = 43. The alkali chromates are prepared from chromite by
first
:
roasting the ore with the alkali carbonate, or mixtures of limestone and alkali sulfate 4FeCr 2 O4 8Na 2 CO3 7C>2
:
The cinder is then crushed 3 + 2 and extracted with water to obtain the chromate. Sodium chromate crystallizes as Na 2 CrO4 -10H 2 O, isomorphous with
= 2Fe 2 O
8Na 2 CrO 4
+ 8CO
the sulfate, and changes to the hexahydrate at 79.5. Potassium chromate, K 2 CrO 4 is isomorphous with potassium sulfate. Sodium dichromate, Na 2 Cr 2 O 7 -2H 2 O, is obtained from the chromate by adding acid and crystallizing from the acid
,
solution.
Above 82,
is
sium dichromate
dichromate,
acid and
the anhydrous salt separates. Potasprepared in a similar way. It is not very
soluble in cold water, but readily soluble in hot.
Ammonium
(NH
4) 2
Cr 2 O7,
is
generally
made from chromic
ammonia. Upon heating, it decomposes according to the equation: (NH 4 ) 2 Cr 2 O 7 = Cr 2 O 3 + N 2 + 4H 2 O. Dichromates are employed extensively in processes requiring a strong oxidizing agent. In the chrome-tanning process, the hide is treated with sodium dichromate, which is then reduced, and chromic hydroxide precipitated in the
pores of the leather. Dichromate forms with gelatine, when exposed to the light, an insoluble product, and advantage is taken of this fact in a number of photographic processes.
Potassium dichromate is important in analytical chemistry in the titration of reducing agents, especially ferrous salts
(cf.
XIX
16).
A number of slightly soluble chromates are important pigments:

e.g.
chrome yellow, PbCrO4; chrome orange, Pb 2
378
REFERENCE
[Ch.
XVII
OCrO
zinc yellow approximately 4 2 O4ZnCrO 4 *3H 2 O. In general, the solubilities of the chromates are very similar to those of the sulfates. 13. Chromyl Compounds. Chromyl chloride, CrO 2 Cl 2 and fluoride, CrO 2 F 2 may be prepared by distilling dichro; ,
,
mate with the

is
alkali halide
and
sulfuric acid.
a blood-red liquid, which
is
The chloride hydrolyzed by water to
Intermediate chlorchromic and hydrochloric acids. chromates also exist, e.g. KCrO 3 Cl, and the halides may be replaced from the chromyl compounds with ammonia to form chromyl diamide, CrO 2 (NH 2 ) 2 14. Peroxychromates. Hydrogen peroxide gives with chromate in acid a deep blue solution of peroxychromate. If this solution is shaken with ether, the peroxy-acid is extracted. This constitutes a very delicate test for chromate
.
or for hydrogen peroxide. The exact composition of the acid is uncertain but appears to be CrO 6 With alkalies it gives
.
which are thought to have formulas such as K 2 Cr 2 Oi 2 At low temperatures in alkaline solution red peroxy-salts such as K 6 Cr 2 Oi6 are formed. From ammoniacal solutions the compound CrO 4 *3NH 3 has been prepared.
salts
.
COMPOUNDS OF MOLYBDENUM
Oxidation States. Molybdenum forms compounds having the positive oxidation states 2, 3, 4, 5, and 6; however, the + 2 and + 4 compounds exist in water solutions only in the form of a few relatively unstable complex ions. Approximate values of the oxidation-reduction potentials for the other states in acid solution are given below.
16.
VOLTS
Mo 4- 3H O - MoOs + 6H+ + 6e~ MoO + + 2H O - H MoO (aq) + 2H+ MO+++ + H O - MoO + 4- 4H+ + 2e~ Mo - Mo*** + 3er
2
-f 2<r
ca.
0.1
0.4 0.0 0.2
ca.
ca.
16.
The
2 State.
The
by heating the
trichloride:
dichloride, MoCl 2 is formed 2MoCl 3 = MoCU + MoCl 4

,
191
SUBGROUP
VI.

in
379
?
*
The bromide may be prepared
a similar manner, and the iodide by heating the pentachloride in hydrogen iodide. These halides are insoluble in water but dissolve in alkalies, and upon acidifying the solution, precipitate the complex bases (Mo 3 4 )(OH) 2 The halides appear to be derivative of the same complex having the formula MoaXe, or [Mo 3 4]-
X2.
They are slowly oxidized by water. 3 State. Solutions of 3 17. The
molybdenum
are
prepared by the reduction of molybdic acid by powerful reducing agents. The color of the solutions is generally an olive green. The hydroxide, Mo(OH)3, (or hydrous oxide) is black, and insoluble in water or excess hydroxide. Upon Ammonium sulfide ignition, it gives the oxide, Mo 2 O 3
.
precipitates the sulfide,
S 3 soluble in excess of the reThe phosphate is also but slightly soluble. Complex agent. ions are formed with halides, and with thiocyanate, e.g. K 3 MoCl 6 and K 3 Mo(CNS) 6 and the colors of these solutions vary from red to violet.
2
,
;
Mo
18.
The
is
4 State.
ore of the element.
The sulfide, MoS 2 is the principal The oxide, MoO 2 forms when the ses,
,
quioxide
heated in air, or the trioxide is reduced with hydrogen (500) or carbon (700). The chloride, bromide, and iodide may be prepared mixed with the dihalide, by
heating the trihalide. These compounds are not soluble in 4 ion is not stable, probably being oxidized water, and the
and reduced to
However, a number of water soluble complex cyanide and halide compounds have been prepared, e.g., K 4 Mo(CN) 8 K4MoO 2 (CN) 4 and
+ MoO 4
"*"1"
and
Mo*4 4
"
".
MoI 4+n.
The
pentachloride, MoCl 6 is made by heating the metal or lower chloride in chlorine. It is the only known oxygen-free compound of this state. In
19.
5 State.
The
water,
2
it
+ H Q = MoOCl + 2HC1. 4 4 or MO + acids, with MoO

4"
"
hydrolyzes to the molybdenyl compound: Mods 3 Compounds of the common

"
are prepared
by the reduction
of
molybdate
in acid solution with moderately strong re-
380
REFERENCE

SnCl 2 The addition
.
[Ch.
XVII
ducing agents,
e.g.
of hydroxide to the
solutions precipitates the hydroxide, may be decomposed to the pentoxide,

test for
MoO(OH)
3,
which
Mo Os. A
2
delicate
the formation of a deep red colored solution upon the addition of thiocyanate, probably Mo(OH) 2 (CNS) 3 Mild reducing agents act upon an excess of molybdic acid with the production of a deep blue precipitate, molybdenum blue, which appears to be a molyb5
molybdenum
.
is
denyl molybdate, (MoO) 3 (MoO 4 ) 2 or (MoO 2 )2MoO 4 In high acid concentration the reduction forms an ion, prob+ A number of ably MoO2 complex chlorides, e.g. MoOCl 6
,
and
MoOCl 4~ are known.

The
a white solid which is soluble, one part in 500 parts of cold water, forming a slightly acid solution. The oxide is formed by roasting
20.
6 State.
The
trioxide,
MoO
3,
is
the disulfide in air, by the igniting of ammonium molybdate, or by the decomposition of a molybdate with hot nitric acid. In the latter case, if the solution is allowed to crystallize
in the cold, yellow
molybdic acid,
H MoO -H
2
4
O,
separates.
oxide forms normal molybdates, e.g. Na 2 4 if fused with basic oxides or carbonates but these especially normal salts are in general unstable, if soluble in water, and tend to form polymolybdates. The complexity of the polyion depends upon the hydrogen ion concentration and the
The
MoO
following values have been given: pH,

4
; .
14-6.5,
6
;
MoO ~
4
2
;
pH, 6.3-4.5, (MoaOn)- pH 4.5-1.5, (Mo 6 O 21 )~ pH, 1.25, 10 and pH 1.0, (Mo 24 O 78 )- 12 Commercial am(Moi 2 O4 i)monium molybdate has a composition which is approx;
imately
(NH
4) 6
Mo O 4H
7
24
O, but
it
may
not be a definite
compound. Lead and the alkaline earth normal molybdates are but slightly soluble, similar to the sulfates and chromates. (Cf. molybdenum orange, XVII 36.) The slightly soluble molybdenyl molybdate has been mentioned above.
compound
of analytical importance
is
.
the
It
ammonium
forms as a
phospho-molybdate,
(NH 4 3 PO4 12MoO 3

)
22]
SUBGROUP
VI.
38J
yellow precipitate, when a solution of ammonium molybdate is added to a solution of orthophosphate in nitric acid.
It is readily soluble in
ammonia
phoric acid,
chloride
ical
and
its solubility is
or alkalies and in phosincreased in the presence of
and many organic acids. Its importance in analytwork lies in its use in separating phosphate from iron
slightly soluble phosphates. The of the precipitate is approximately as written, composition
and other ions which form
but
may
contain slightly less
MoO
3,
depending on the conare likewise

of the
ditions of precipitation.
Rubidium and thallium phosphomolybdates

insoluble in nitric acid, as are also salts of
many
:
heavy metals, if the solutions are not too acid. A number of other phosphomolybdate complexes also exist for example, the compound, (NH 4 )6(PO 4 ) 2 '5MoO3'7H 2 O, crystallizes from the solution formed by dissolving the ordinary precipitate in excess ammonia. 21. Normal molybdates form with hydrogen peroxide the red peroxy-acid, H 2 MoO 8 and salts of this peroxy-acid have been prepared. With the polymolybdates more complicated
,
peroxy-acids are formed.
The trioxide acts toward strong acids as a basic oxide with

;
forms the somewhat volatile oxychlohydrochloric acid ride, MoO(OH) 2 Cl 2 and with sulfuric acid the oxysulfate, MoO 2 SO4 Oxybrom compounds also form, but the iodine compounds are not stable. Fluorine forms a hexahalide, MoF 6 when the metal is heated in the halogen. Hydrogen sulfide gives with an acid solution of molybdates a precipitate of the sulfide, MoS 3 This compound is soluble in excess ammonium sulfide with the formation of
it
; .
,
thiomolybdate.
COMPOUNDS OF TUNGSTEN
Oxidation States. Compounds are known containing tungsten with the positive oxidation numbers 2, 3, 4, 5, and 6. The + 6 compounds alone are of importance. In
22.
382
REFERENCE
[Ch.
XVII
alkaline solution the tungstates ( 6) are very stable, but tungstic acid in the presence of hydrochloric acid is reduced by stannous chloride to a blue compound, probably
and stronger reducing agents, e.g. tin, will 4" 4 reduce the solution to (green), and upon further "" 44 action to complex ions of probably W(OH)C1 4 (red 43 brown color), and of 2 Cl9 (reddish probably blue). The following potentials are only approximate and
2
(WO )2(WO
4 );
WO
"
"
"
W
,
"
are considerably modified in the presence of halide ions.

VOLTS
26
W = W+++ + 3eW+++ + 2H O = WO + 4H+ + e2WO + H O = W O + 2H+ + 2e~ W O + H - 2W0 + 2H+ + 22
< >
6 3
WOClr + H O 2
WO C1 + Cl- + 2H+ + e~
2
3
0.05 0.05 0.0

0.15 0.26
23.
The
Compounds.
The
halides,
WC1
2,
WBr
2,
WI
2,
have been prepared by the action of reducing agents
upon higher halides at high temperatures. The chloride is somewhat soluble in water, but the solution hydrolyzes to some complex substance; the compound 3 C1 7 -4|H 2 O
HW
has been obtained from alcoholic solutions.

24.
The
Compounds.
have been prepared by the of the general formula, 3 2 C1 9 reduction of tungstic acid with tin, but no simple com,
RW
Alkali and
ammonia
salts,
indicate that the ion
known. Crystal structure data C1 9 )~3 has an interesting structure. (W 2 Six chloride ions form an octahedron about the tungsten as indicated in the following diagram
pounds of
this valence are
:
Cl
\ / \ / Cl W Cl W Cl / \ Cl/ \Cl Cl
25.
Ci
Cl
Xhe
4 Compounds.
The
dioxide,
WO
2,
is
formed
by heating the trioxide in hydrogen, but if too high a temperature is employed the oxide is reduced to the metal.
27]
SUBGROUP
oxide
is
VI.
ETC.
383
The
also a product of the hydrolysis of the tetraIt is readily oxidized,
chloride, or of tetravalent solutions.
and with
iodide
alkali evolves
only slightly soluble in may be prepared at high temperatures, but they are readily hydrolyzed by water. The complex cyanide ion, ~ W(CN) 8 4 is stable in water solution, and many of its salts have been prepared. The sulfide, forms when the 2 trisulfide is ignited. The compound is not soluble in water
,
hydrogen and forms tungstate. It is acids. Anhydrous tetrachloride and
WS
or dilute hydrogen ion.

26.
The
bromide,
in water,
+5 WBr
halides in
Compounds. The chloride, WC1 5 and 6 are formed by carefully reducing the hexahydrogen. The compounds are readily soluble
, ,
forming light green solutions which contain the or 2 +; with excess halide the solution appears to form complex halides such as WOC1 6 Similar solutions are formed by the cathodic reduction,
ions
WO ++ +
WO
or reduction by tin of alcoholic solutions of tungstic acid in
When oxalic acid is used, complex hydrochloric acid. oxalates are formed, e.g. Na3WO2(C 2 O 4 )2. Compounds of ~ the complex cyanide ion W(CN) 8 3 are known. The addition of ammonia to solutions of the complex The sulfide chlorides precipitates the hydroxide W(OH) 6 is not known. Stannous chloride gives with tungstic acid a blue precipi.
tate,
tungsten blue, which probably has the composition

2) 2
(WO
WO
4.
+ 6 Compounds. The yellow trioxide, WOs, occurs as the mineral wolframocher. It is readily prepared by gently igniting the acid, which is obtained from its salts by digestion with hydrochloric acid. In the cold, the hydrated acid, 2 2 O, separates, while in hot solutions, 4 the anhydrous acid precipitates. The former is somewhat
27.
The
H WO H
soluble in water, but the latter neither dissolves in water
nor any acid, except hydrofluoric. The trioxide also forms many polytungstates.
Thus,
384
REFERENCE
[Ch.
XVII
compounds with sodium oxide of the general formula (Na 2O) n (WO3) m are known, in which, when n = 1, m may vary from 1 to 6; and more complicated compounds in which both n and m are large numbers. Except for a few of
the alkali compounds, the tungstates are not soluble in water. Although the normal sodium salt, Na 2 4 *2H 2 O, is the commercial "tungstate of soda" is readily prepared, This salt is emthe paratungstate, Nai Wi 2 O 4 i'28H 2 O.
WO
ployed as a mordant in dyeing. Like molybdenum, the trioxide forms a number of phosis used as a 3 PO 4 *12WO 3 photungstic acids. The acid,
reagent to precipitate alkaloids and proteins.

also forms silicotungstic acids: e.g.
The
4
oxide
by
boiling silica
with
ammonium polytungstate, the compound, (NH ) 8SiWioO3 6 8H 2 O, is obtained. When a solution of sodium paratungstate is boiled with
hydrogen peroxide, the solution is found to contain the peroxytungstate, NaWO 4 H 2 O, and many complicated compounds have been obtained.
Tungstates are converted by alkali sulfides into thiotungstates, e.g.
(NH 4 )
WS
is
when
,
these solutions are acidified,
the trisulfide,
WS
3,
WC1 6 and WBr 6 result from the 6 hexahalides, action of the halogens upon the heated metal. The fluoride is also formed by the reaction: WC1 6 6HF = 6
The
>
WF
precipitated.
6HC1. The oxyhalides, 2 2 and 4 may also be prepared. The fluorides, and also the trioxide, are soluble in excess of fluoride to form complex ions, e.g. W02p4
,
WO X
WOX
WF
.
28. Analytical.
In the
it is
systematic
is
metallic elements, num group in that
chromium
by
4
the separation associated with the alumiof

2 S in 0.3 AT H+, S as Cr(OH) 3 (NH 4 ) 2 nitric acid and treated
.
not precipitated by
but
is
precipitated
NH OH
is
and
When
this precipitate
dissolved in
with sodium peroxide, the chromium remains in solution as Na 2 CrO 4 Chromium may be identified by the precipita.
tion of lead chromate from dilute nitric acid solution.
29]
SUBGROUP
VI.
ETC.
385
<?
Molybdenum
tated
by
in
resembles antimony in that it is precipiQ.3N H+ and the sulfide is soluble in am,
monium
sulfide to
sulfide
form the
thio-salt.
The
filtrate
is
precipitation, however, hydrogen through the reduction of some of the molybdenum. In the absence of phosphate, MoO 3 remain as a residue when molybdenum compounds are evaporated with the and the product washed with acids, HNO 3 + HC1O 4 water. The oxide is soluble in hydrogen fluoride, and the hydrated oxide, H 2 MoO 4 is soluble in 2N HC1.
,
from the colored blue
Tungstate gives a precipitate of tungsten blue with stannous chloride in dilute HC1; and molybdate gives a precipitate of molybdenum blue with stannous chloride in 127V HC1, and an orange color (Mo4 5 ) in dilute acid. The Mo45 solution forms, with KCNS, a deep red color of
"
MoO(CNS)
may
3.
In gravimetric analysis, the following pure
compounds
,
be separated and weighed: Cr 2 O 3

4,
BaCrO 4
MoO
3,
PbMoO
salts,
and
WO
3.
The
trioxides of
molybdenum and
may be separated by precipitating the mercurous which are then ignited to the oxide. In volumetric analysis dichromate may be titrated against ferrous ion, or an excess of iodide may be added to dichromate in acid, and the iodine titrated with thiosulfate. + Molybdates may be reduced to MoO 2 with hydrogen iodide, and the iodine determined with thiosulfate, or the 44 4 by zinc, and the molybdate may be reduced to Mo product titrated with permanganate.
tungsten
"
"
29. Potential
Diagrams.
In order to compare the trends
in the oxidation-reduction potentials of the elements of this group, the following diagrams are given.
0.86
0.41
Cr+++
1.36
Cr
Cr++
(0.2)
Cr2 O7
(0.0)
Mo
Mo+
MoO
0.0
(-
0.4)
<
0.05
W+
>
3
0.05
MoOa(aq)
0.03
WO
W0
(S)
Chapter XVIII
SUBGROUP
VII.
AND RHENIUM
MANGANESE, TECHNETIUM,
1. The elements of Subgroup VII are manganese, technetium, and rhenium. The discussion of the relation of atomic structure and oxidation states of the elements of
Subgroup VI
Subgroup VII except, of course, that these elements possess one more electron. In the + 7 state they show certain resemblances to the perhalates, but in the lower states they are more closely related to the elements of neighboring atomic numbers. These latter relations are further discussed in Chapter XIX. 1 state. Rhenium may be reduced to the This seems most remarkable, since octet formation is otherwise
is
also applicable to
restricted to s-p electron groups.
Occurrence. Manganese is ranked 9th among the metals in order of abundance, the estimated percentage in
2.
igneous rocks being 0.10. The principal ore is pyrolusite, MnO 2 Other minerals are braunite, 3Mn 2 O 3 -MnSiO 3 rhodomanganite, Mn 2 O 3 -H 2 O; hausmannite, Mn 3 O 4
.
chrosite,
MnCO
alabandite,
MnS;
hauerite,
MnS
iron.
2.
The
manganese ores are generally associated with
The
evidence
is fairly
element number 43
definite that there is no isotope of of sufficient stability to exist in nature.

first
Radioactive isotopes were
prepared in 1937 by the
bombardment
in a cyclotron.
of
molybdenum with deuterons accelerated The previously suggested name of masurium

386
has
now been
replaced by technetium, derived from the
3]
SUBGROUP
VII
'
387
"
',
Greek word this was the

means.
years)
is
for "technical" in recognition of the fact that
first new element to be produced by technical The most stable isotope Tc" (half-fife 9.4 X 10 5
a product of the slow neutron
fission of
uranium
per cent. A uranium pile operatat a power level of 10 5 kw produces about 4 grams of ing Tc" per day. The abundance of rhenium is quite low. The first commercial production, around 1935, came from the potash residues (now exhausted) in Germany. A small domestic
and the
fission yield is 6.2
production has been developed from "flue dust" containing molybdenum sulfide in an Arizona copper smelter. 3. The Metals. Manganese is difficult to prepare in the state by reduction with carbon, as it forms a series of pure It may be presolid solutions with the carbide, Mn a C. reduction of the oxide by aluminum. The pared by the production of the metal by electrolytic reduction has
The electrolyte is developed rapidly in recent years. sulfate with a high concentration of ammonium manganous sulfate. Manganese is an essential constituent of most of the domestic steels; the average consumption is 12 pounds of manganese per ton of steel. It is used to deoxidize the molten metal. This property depends in part upon the very
molten
slight solubility of the manganous oxide and sulfide in It also improves the rolling and forging iron.
qualities of the steel
and contributes toughness.
For
this
purpose ferromanganese (70-80 per cent Mn) and, to a lesser extent, Spiegel iron (15-25 per cent Mn) are employed. These iron alloys are prepared by reducing the mixed ores in a blast furnace. The annual consumption of manganese in the steel industry is around a million tons of
35 per cent ore and about 90 per cent of this is imported, principally from India, Brazil and Africa. The pure metal is reddish-gray, and relatively soft compared to iron, but if it contains carbon, it is very hard and The melting point is lower than those of either brittle.
388
REFERENCE

TABLE
I
[Ch.
XVIH
ATOMIC AND PHYSICAL PROPERTIES OF ELEMENTS OF SUBGROUP VII
tarnishes readily in moist contains the carbide, which 3 C, evolves methane and hydrogen with water. Manganese bronze contains about 34 per cent Mn, 60 per cent Cu, and 35 per cent Zn. The alloy manganin
iron or
air,
chromium.
if
The metal
especially
it
Mn
of resistance
TcO 4~
Ni 4) has a very low temperature coefficient and is used in electrical instruments. Small amounts of manganese are added to many aluminum alloys. Technetium metal may be precipitated from solutions of
(Cu
84,
Mn
12,
It electrolytically or by the action of Fe or Cu. has also been prepared by the reduction of the sulfide by C. 2 at 1000 Rhenium metal may be prepared by electrolytic precipitation from water solution of the perrhenate. In contact with water it is readily oxidized back to the perrhenate. The metal is somewhat soft and ductile in spite of the
extremely high melting point.

uses at present.
4.
There are no commercial
Reactions of the Metals. The electropositive nature (Par. 5) of manganese renders it highly reactive toward oxidizing agents. The principal reactions are given in Table II. Rhenium is less electropositive than manganese and is not oxidized as readily by weak oxidizing agents, but moderately strong oxidizing agents will carry it all the way up to the perrhenate. By direct reaction with the elements
5]
SUBGROUP
,
VII
389
metallic
ReS 2
rhenium forms Re 2 O7 ReF 6 ReCl 4 ReBrs, and Technetium is not oxidized by HC1.
,
TABLE
3Mn + 20 2 = Mn O
3
II
REACTIONS OF MANGANESE
4
Heated
2
2 2
in air
Mn Mn Mn Mn
+ 2H+ = Mn++ + H + 2H O = Mn(OH) + H + X = MnX + S = MnS 3Mn + C = Mn C

2
2
Slowly in cold
X=
halogen.
F2
also gives
MnFa
lOMn
+ 3N
= 2Mn 6 N>
2
Heated together High temperature. With Si forms MnSi and Mn 2Si Burns in N 2 at 1200. With P forms Mn 6 P 2 and MnP
2Mn+4KOH+3O
==2K 2 MnO4+2H 2O
COMPOUNDS OF MANGANESE
5.
Oxidation States.
ing the positive oxidation states two lower states are basic, the three higher states acidic.
Manganese forms compounds hav2, 3, 4, 5, 6, and 7. The + 4 amphoteric, and the

There
is
evidence for the
complex cyanide,
e.g.,
K Mn(CN)6.
5
:
The
oxidation-reduc-
tion potentials relating to the various states are in the following potential diagrams
summarized
Basic Solution
0.59
1.57
-0.1
-0.2
Mn
-0.8
8
Mn(OH) 2
|
Mn(OH)g
0.04
MnO2
||
MnO - 60
-0.3
MnO4~
|
-0.56
MnO4~
|
A
of
of very important relations in the chemistry manganese may be correlated with these values:
number
unstable even at very low concentrations in respect to the decomposition: 2Mn~hH
Manganic
2
ion,
Mn" "^,
1
is
"
+ 2H O
= Mri++
+ MnO + 4H+.
2
390
REFERENCE

,
[Ch.
XVIII
dioxide
solution,
when acidified, decomposes to the Manganate, MnO 4 and permanganate: 3MnO 4 + 4H+ = MnO 2 ~ + 2MnO 4 + 2H 2 O. For the equilibrium in~ alkaline ~~ =
3MnO
K
of
2H 2 O
MnO + 2MnO
2
4OH,
~ to MnO 4 may be large. MnC>4 Permanganate in acid solution will oxidize manganous ion to the dioxide, and in alkaline solution will oxidize
16.
Hence
at high concentrations of OH~~, the ratio
the dioxide to manganate. Manganese dioxide in concentrated acid, and permanganate in both acid and alkali, will slowly evolve oxygen from water. With concentrated acid the reaction of permanga-
nate
is
explosive.
Oxygen in normal alkali is not capable of oxidizing the dioxide to manganate, but the reaction does occur in fused potassium hydroxide. Mn(OH) 2 is readily oxidized by
to
Mn(OH) 3
Excess of a reducing agent upon permanganate in acid solution yields manganous ion; but in alkaline or neutral solution the product is the dioxide. Partial reduction of
permanganate
duction of
in alkaline solution gives

4
probably
in high
6.
MnO MnO
3~~,
manganate. Reforms a compound of the + 5 state, but this state is relatively unstable even
first
OH~
and the reduction proceeds to
MnO
2.
Manganous Ion. Compounds of the + 2 state are known as manganous. They resemble magnesium and
ferrous iron in their solubility relations, and are in general characterized by a delicate pink color. The hydroxide,
Mn(OH)
are
2,
forms when alkali or

it is
ammonium
added to a manganous
soluble in
solution.
hydroxide,
droxide,
ammonium
hydroxides Like magnesium In the air, it salts.
quickly darkens through the oxidation to manganic hyMn(OH) 3 or possibly MnO-MnO 2 -nH 2 O. When heated in the absence of air, the hydroxide forms the oxide,
,
MnO; and
Alkali
this,
heated in
air, is
oxidized to
Mn O
3
4.
and ammonium carbonates precipitate the car-
7J
SUBGROUP
VII
391
bonate,
MnCOs.
This, like the hydroxide,

ion.
is
soluble
ir
excess~ammonium
sulfides, is
MnS, though precipitated by soluble soluble in dilute acids. The moist solid readily oxidizes, upon standing in the air, to the sulfate.
sulfide,
The pink
The
and the
sulfate, nitrate, halides, and cyanide ate soluble; ~ last forms the complex ions and 3
Mn(CN)
Mn(CN)e
hydrated
sulfate crystallizes in a number of forms, a transition from the penta-hydrate to
The
the tetra-hydrate occurring at about 26. It forms double 2 SO 4 -MnSO 4 -6H 2 O, salts, such as isomorphous with the
corresponding
,
salts of
magnesium.
,
The ammonium phosphate, NH 4 MnPO 4 ferrocyanide, Mn 2 Fe(CN) 6 and oxalate, MnC O 4 '2H O, are but slightly
2 2
work. Reference has been 7. Manganese made in the preceding paragraph to the formation of the hydroxide, Mn(OH) 3 (probably hydrous oxide), by oxidaDue to the instability of tion of manganous hydroxide. Mn f~H~ (Par. 5), the only compounds the manganic ion, which can be prepared from water solutions are slightly soluble, or slightly dissociated. The trifluoride may be prepared by the action of fluorine upon the metal, and the trichloride by the decomposition of the tetrachloride. In water, they decompose, e.g. 2MnF 3 MnO 2 4H+ but a deep red 2H 2 O = Mn++ 6Fsoluble,
in analytical
and are of importance

in the
3 State.
solution containing the complex fluoride, 2 6 may be prepared by dissolving the hydroxide in excess of potassium acid fluoride. There is evidence of the formation of some
,
K MnF
MnCl when
B
the dioxide
is
treated with concentrated
hydrochloric acid. Powerful oxidizing agents in concentrated hydrochloric acid oxidize manganous ion to the complex chloride. The hydroxide in sulfuric acid forms an unstable sulfate, and alums have been prepared. Powerful convert manganous ion, in 4 oxidizing agents, e.g., excess acetic acid, into manganic acetate.
KMnO
392
REFERENCE

The chemistry
of
[Ch. XVIII
8.
Manganese Dioxide.
pyrolusite,
it
ganese deals largely with the dioxide,

eral,
is
MnO
2.
manAs the min-
+4
element.
dioxide;
teric, it is
In
many
the most important source of the respects, the dioxide resembles lead
although essentially amphotoward both acids and bases. In cold concentrated hydrochloric acid, the oxide dissolves slowly to form a green solution of the tetrachloride, and the hydrous dioxide may be reprecipitated from this solution but upon heating, chlorine is evolved and manganous chloride formed. The sulfate may also be obtained in solution, but it is very unstable toward the evolution of oxy-
and
like the latter,
comparatively inert
gen.
A complex fluoride, K MnF

2
6,
however,
is
more
stable.
oxide does not dissolve readily in alkali, but manganites are formed by fusing the oxide with certain basic
The
oxides.
oxidizing
CaMn 2 O 5 is prepared by manganous oxide with bleaching powder, and potassium manganite, K 2 Mn 6 On, by passing carbon dioxide into potassium manganate solution. The oxides, Mn 2 O 3 and Mn 3 O4, may be considered as manganous manganites; upon heating, the dioxide loses oxygen to form these oxides
Calcium manganite,
,
or possibly solid solutions of the type (MnO) n (MnO 2 ) m The oxidation-reduction potentials of the dioxide have
.
been discussed in Paragraph
5.
in the paint and varnish to catalyze the oxidation of oils by oxygen, i.e. industry the drying process. The glass industry employs the dioxide
Manganese dioxide
is
employed
to neutralize the green color of ferrous silicate impurities. The largest use (about 30,000 tons in U. S. annually) of
the dioxide
is
as the oxidizing constituent of the ordinary
dry
cell.
9. "Dry Cells." The dry Leclanche battery, generally called the "dry cell," consists of a zinc anode, a cathode of carbon packed in manganese dioxide, and an electrolyte of ammonium chloride solution, containing a little zinc
chloride,
which
is
held in a porous solid (kieselguhr).
The
111
SUBGROUP
VII
393
anode reaction is Zn + 2C1~ = ZnCl 2 (s) cathode reaction, MnO 2 + NH 4+ + 2H 2 O
+ 2e~~\ and the + e" = NH OH

4
Mn(OH) Large currents cannot be drawn from the cell, owing to the polarization of the cathode, possibly due to the slow diffusion of the elec3.
The voltage
is 1.48.
The ordinary dry cell does not function below 20 C., but the addition of LiCl or CaCl 2 to the elec40 C. trolyte extends the range to Several other types of "dry" batteries are in use.
trolyte.
A Mg-AgCl on Ag Mg + 2AgCl = MgCl +

2
cell
employs
the
reaction,
2Ag. rated by a sheet of filter paper and moistening the paper with salt water.
1.3 to 1.5 volts.
The
electrodes are sepathe cell is activated by
The
potential
is
The
reaction,
AgO + Zn + KOH = Ag
used in a cell which is stored dry and is activated by the addition of KOH. The voltage is 1.5. Cell-s employing atmospheric oxygen on activated charcoal as the cathodes are increasing in importance. The anode is generally amalgamated zinc and the electrolyte, NaOH
2,
+ KHZnO
is
or
Ca(OH) 2
2
The anode
reaction
+ H O + 2e~ and the cathode = HO + OH~~, followed by the

"~
2
+ 3OH~ = HZnO reaction, O + H O + 2e~

is
Zn
"~~
catalytic decomposition
of the
10.
HO2~.
The
+
.
potential is around 1.3 volts. 5 State. Manganese dioxide in fused
The
KOH
absorbs oxygen to give a ratio of 2.5 oxygens per manganese, The careful electrolytic reduction of mani.e., Mn 2 O 6 in OH~ gives a blue solution which disproporganate tionates in a few minutes into the dioxide and manganate.
0AM
The reduction
the dioxide.
11.
of
manganate
in 0.01
M OH~ goes directly to

dioxide
is
Manganate.
2
When manganese
3
2 4 2
fused with
potassium hydroxide, some decomposition occurs:
3MnO
In the presence of air or other oxidizing agents, as potassium chlorate, the manganese is all oxidized to manganate: 2MnO 2
+ 2KOH = Mn O + K MnO + H
O = 2K MnO 4
2
O.
+ 4KOH
+ 2H
O.
The potassium compound
is
394
REFERENCE
[Ch.
XVIII
salt
soluble in water, giving a green solution, from may be crystallized. Manganates are
which the
somewhat
similar in solubility to sulfates. The free acid cannot be prepared because of the decomposition into the dioxide
~ and permanganate: 3MnO 4 + 4H+ = MnO 2 + 2MnO 4 + 2H 2 O; but the very unstable trioxide has been prepared by the reaction: (MnO 3 ) 2 SO 4 + Na 2 CO, = Na 2 SO 4
+ 2MnO + CO +
3 2
Ô 2
the concentration of hydroxide in a manganate solution is decreased, the color changes from green to purple with the formation of permanganate
Paragraph 6 for the manganate. 12. Permanganate.
Reference should be made to oxidation-reduction relations of
When
and the dioxide:
3MnO
+ 2H O = 2MnOr + MnO
2
4OH~~.
The conversion
may
also be carried out
alkaline solution: e.g.
2MnO
manganate permanganate by powerful oxidizing agents in ~ =

4
of
into
+ CRT + H O
2
2MnO
+ cr +
A
20H-.
solution of permanganic acid, 4 may be prethe reaction of dilute sulfuric acid and barium pared by
,
HMnO
2
permanganate, or by the oxidation of manganous sulfate
by lead dioxide:
2MnSO + 5PbO + 3H SO = 2HMnO 4

4
2
5PbSO
+ 2H
2 O.
The
solution decomposes
ing, or in the sunlight.
When
upon boilpotassium permanganate is
treated with cold concentrated sulfuric acid, the solution turns green through the formation of the sulfate, (MnO 3 ) 2 -
and upon the careful addition of v cold water, the heptoxide, Mn 2 O7, separates as a dark brown, highly ex4
;
SO
plosive liquid Alkali permanganates are usually prepared commercially by fusing the dioxide with alkali hydroxide in air to form
the manganate, followed

alkaline solution.
by oxidation with chlorine in the They may also be prepared by the anodic
oxidation of manganate. If a pure permanganate is desired, the potassium salt is generally employed instead of the sodium salt, as the great
15]
SUBGROUP
VII
395
s
solubility of the latter renders
it difficult
to prepare
fre<$
from impurities. Alkali permanganates are used as disinfectants (Condy's Liquid), as oxidizing agents in industrial processes, and as volumetric reagents (Par. 15).
COMPOUNDS OF TECHNETIUM
Oxidation States. Detailed information on the In general the chemistry of technetium is still lacking. chemistry is intermediate between that of manganese and rhenium but it appears to resemble the rhenium more than ~ manganese. The ion TcO 4 in acid is a fair oxidizing agent and is reduced to the metal by Sn or Cu Tc + 4H 2 O
13.
:
- TcO 4~+
dence for a
8H++
1
7e~
E =
ca.
-0.5.
There
is
no
evi-
Tc ++ appears to be stable in water solution and the dioxide TcO 2 is a much weaker oxidizing agent than MnO2.
state.
COMPOUNDS OF RHENIUM
Rhenium forms the oxides Re 2 O 3 Re 2 O 7 and claims have been made for the ReO 2 ReO 3 formation of Re 2 O. Halides or complex halides are known
14.
Oxidation States.
,
5, +6, corresponding to the oxidation states +3, +4, 7. and When perrhenate is reduced in acid solution with zinc, eight equivalents of oxidizing agent are required to oxidize the solution, and this constitutes evidence for the
existence of rhenide ion, Re~.
The
following potentials are

VOLTS
only approximate:
2H + ~ O = ReO + 4H+ + 4<r ReCl + 4H O = ReOr + 6Q- + 8H+ + 3<r Re" = Re + e~ Re0 + 2H = ReOr + 4H+ + 3e~
2
Re Re
-f
H O = ReOr + 8H+ +
2
7<r
ca. ca.
0.365
0.25
0.5 0.4
0.51
16. Perrhenate. The oxide, Re 2 7 is colorless and dissolves readily in water to give the solution of perrhenic acid, The potassium, silver, and thallous salts are but 4
,
HReO
slightly soluble.
So-called "mesoperrhenates," e.g.,
Ba 8 -
396
REFERENCE
[Ch.
XVIII
(ReO 5 ) 2 are formed with excess base. The acid is a poor oxidizing agent (Par. 12) but in the presence of hydrochloric acid it is somewhat more powerful because of the formation
,
of the
and will oxidize iodide. The complex ion ReCl 6 sulfide, Re 2 S 7 is precipitated by H 2 S in ammonia solution and is soluble in excess sulfide with the formation of thio,
perrhenate,
16. ions,
ReS 4~~. The Lower Oxidation

,
States.
The complex
chloride
ReCle" and ReCl 6
may be prepared by the reduction
of perrhenate in hydrochloric acid. The former is green in 5 complex The color and the latter a yellow brown.
is
is
stable in high chloride although the compound ReCl 5 ~ said to decompose in water into ReO 4 and ReCl 6
trioxide
is
The
soluble in hydroxide, but the solution is unstable with respect to decomposition into ReO 4 and
2.
,
However, the barium rhenate, BaReO 4 has been described. The dioxide is amphoteric but somewhat inert to both acids and bases. The hydrous sesquioxide is preThe sulfide, cipitated by hydrolysis of the trichloride. ReS 2 is formed when Re 2 S 7 is heated. The highest fluoride which has been reported is ReF 6 The compounds K 2 ReF 6 ReOF 4 and ReO 2 F 2 have been prepared. 17. Analytical. Potassium permanganate is the most
,
ReO
widely used oxidizing agent in volumetric analysis. Its importance depends upon its ability to oxidize quantitatively a very large number of substances. These include the direct oxidation to a higher oxidation state of ions or compounds of Fe++, Mn"-, Cu+, Sn++, As^, Sb+++, Ti+++, Mo+3
the oxidation of the inorganic acids and HCNS; the oxidation of 2 S, 2O2 2 2 SO 3 acids or their salts, such as oxalic and formic acids. organic In addition to these determinations by direct oxidation, many methods of indirect determinations have been worked
, , ;
45
"
U4
,
"
and V+4
,
HNO H
out, such as the precipitation of Ca, Sr, Ba, Cu Pb, Zn, Hg (ous), Ce, and La as oxalates, and the subsequent
r
oxidation of the oxalic acid the determination of phosphate

;
17]
SUBGROUP
VII
397
by the precipitation of (NH 3 )3PO 4 -12MoO 3 and the 444 and reoxidasubsequent reduction of the MoO 3 to Mo tion; the determination of potassium by precipitation with cobalt nitrite and the oxidation of the nitrite; and the standardization of Na 2 S 2 O 3 solution by the addition of a
, "
known weight
titration of the
of
I2
KMnO
to excess
liberated
oxidizing agents, e.g. PbO 2 addition of a known excess of a reducing agent, e.g.
I"~, followed by the the thiosulfate. Powerful by may be determined by the
Fe+
"*~
and
:
its titration
by permanganate.
In acid solution, permanganate is reduced to manganous 8H+ Se~ = Mn++ 4H 2 O. Since 5 equivion 4 alents of electricity are involved, a one normal (one equiv-
MnO +
of oxidizing power) solution of permanganate is defined as 1/5 molal, when it is to be employed in the above Commercial potassium permanganate is not of reaction.
alent
purity to permit standardization by directly out the salt; hence the solution is generally standweighing ardized in terms of one of the following primary standards:
sufficient
sodium oxalate, oxalic
pure iron, or ferrous am4 -6H 2 O. One of the advantages of permanganate is that the distinct color change of the reaction serves as an endpoint indicator. However, care must be taken in titrating a reducing agent with permanganate not to approach the endpoint too rapidly, as excess of the reagent may react; with
acid,
4
monium
sulfate,
(NH
4) 2
SO -FeSO
manganous
ion to form
compounds
of
Mn4
"
or
is
Mn+4
which might not be completely reduced. In alkaline or neutral solutions, permanganate ~ =

to the dioxide:
reduced
MnO
2H O
2
3e~
MnO +
2
4OHT;
hence a normal solution of permanganate for use under these conditions is defined as 1/3 molal. One of the important applications of this reaction
is
in the titration of
manganous
salts in
neutral solution:
3Mn~H
2MnO4~"
it
2H O = 5MnO 2
2
+ 4H+.
may
In the gravimetric determination of manganese,
398
REFERENCE
[Ch. XVIII
be precipitated as the ammonium manganese phosphate, and ignited to the pyrophosphate. Manganous compounds may also be precipitated as the dioxide by strong oxidizing Upon agents, bromine water frequently being employed. the dioxide yields Mn 3 O 4 Gravimetric determinaignition, tion may also be carried out with the manganous carbonate
.
and
sulfide.
In the systematic scheme of qualitative analysis, manganese is associated with the group thrown down by ammonium sulfide (Append. VI). A very delicate confirmatory test is the formation of a purple permanganate color when a very small concentration of manganous is boiled with lead dioxide and concentrated nitric acid.
Rhenium
and
element
is
precipitated as the sulfide in acid solution
like stannic sulfide is soluble in excess of sulfide.
The
may be determined by precipitation of the slightly soluble AgReO 4 or TlReO 4 and also by precipitation with
,
8-hydroxyquinoline.
Technetium may be separated from rhenium by the

electrolytic reduction of the pertechnetate in alkaline solution to the dioxide, as under these conditions rhenium
does not precipitate.
Chapter
XIX
IRON, COBALT,
1.
AND
NICKEL
" "transition series, in which the electrons in the third quantum state (Append. XVIII) are being in-
The
first
is complete with copper; and the three preceding elements, iron, cobalt, and nickel, constitute a triad possessing many common properties, as might be expected from the fact that the differences in behavior are due merely to the number of d electrons. The free elements are metals of similar appearance, melting point, density, and other physical properties. They show marked resemblance to all the members of the transi-
creased from 8 to 18,
tion series, although a gradual change in properties noted between titanium and nickel (Table I).
may
be
The three metals are readily oxidized to the + 2 state, but the removal of an additional electron to form the + 3 ion becomes increasingly difficult with increasing atomic
number: thus,
a good oxidizing agent; cobaltic ion a very powerful oxidizing agent and nickelic ion is not known. The + 2 ions are similar in properties to the corferric ion is
;
responding ions of other elements of the series, especially the adjacent elements, as has been pointed out under
chromium and manganese.

Powerful oxidizing agents acting in alkaline solution form which the elements are in the + 4 state, or, in the case of iron, the + 6 state. These are the highest states shown by the group and in this respect they are intermediate to chromium and manganese, on the one hand, in which
salts in
399
400
REFERENCE

TABLE
[Ch.
XIX
FIRST TRANSITION SERIES
* This oxide may be a mixture of higher and lower oxides, t Oxide known only in compounds.
all of the "transition" electrons may be removed, e.g. in chromate and permanganate, and to copper and zinc, on the other hand, in which one and none, respectively, of the electrons of the 18 group may be readily removed. These relations are further summarized in Table I. Another important characteristic of iron, cobalt, and nickel is the tendency to form complex ions. This property has been discussed in Chapter VII as related to the very high fields of force existing about the "18 electron kernel type of ion, and since these transition elements are ap7 '
proaching to this structure, it is not surprising that they also possess this property to a high degree.
A number of relations between iron, cobalt, and nickel, and the corresponding members of the second and third
transition series, are discussed in connection with these elements, Chapter XX, but in general the "horizontal"
3]
IRON, COBALT,
AND
NICKEL
401
e.g.,
periodic relations are more marked than the "vertical/* iron resembles cobalt more than it does ruthenium.
IRON
The average percentage of iron in the 2. Occurrence. igneous rocks is given as 5.01. The percentage is doubtless higher in the low lying basaltic rocks, and the central core of the earth (diameter about 2,500 miles) is largely iron. The metallic meteors are generally over 90 per cent iron.
Among
the elements of the earth's crust (outer ten miles)
iron ranks only fourth in abundance.
The free metal is rarely found on the earth's surface, and then the specimen is generally of meteoric origin. Igneous rocks contain ferrous silicates isomorphous with magnesium Table VI); ferric silicates as [Mg, Fe]SiO 4 (cf. XIV
ous
alumino-silicates as orthoclase, K[A1, Fe]Si 3 O 8 and numersulfides, the more important being pyrrhotite, FeS(S) x>
;
and
pyrites,
FeS2
of the igneous rocks has resulted in the formation of deposits of oxides and carbonates which are
The weathering
the commercial source of the metal.
The
principal ores are:
hematite, Fe 2 C>3; brown ore, Fe2O3nH 2 O, including limonite, 2Fe 2 O 3 *3H 2 O; magnetite, Fe 3 4 and siderite, spathic iron
;
or "kidney ore," FeCO 3 In addition to the above, hundreds of minerals are known containing iron in combination with practically all of the
.
acid oxides, and with the sulfides and compounds of other positive elements. Iron is also an essential constituent of
the haemoglobin of the blood. 3. Pure Iron. Iron is tetramorphous the transition tem;
peratures between the forms are given in Table II. A-iron, called ferrite, is a soft, tough, grey- white metal. The crystal lattice is the body-centered cubic type; the metal is highly
iftvolve
paramagnetic. The transition from a- to /3-iron does not a change in the lattice structure, and appears to be
402
REFERENCE
[Ch.
XIX
largely electronic in nature, as the unusually high magnetic The total permeability of a-iron disappears in /3-iron. absorbed in the transition is small, and the change energy appears to start many degrees below the recorded transition
point.
TABLE
II
ATOMIC AND PHYSICAL PROPERTIES OF IRON
F-iron
of-form.
is but slightly magnetic in comparison to the Its lattice structure is face-centered cubic. T-iron
forms solid solutions with iron carbide, and these may be obtained at room temperature in a metastable state by
rapid quenching.
under
5-iron.
Steel.
Little is
The importance of this fact is discussed known regarding the properties of
is of only slight commercial importance. It be prepared by heating the oxide in a current of hymay drogen, and by the electrolysis of ferrous sulfate solution. In both of these preparations, the iron contains absorbed
Pure iron
hydrogen which may be removed by heating in a vacuum. The hydrogen appears to dissolve to form a true solution; the same is true of nitrogen and other gases at higher
temperatures.
4. Metallurgy of Pig Iron. The basic principle involved in the smelting of iron is the reduction of the iron oxides by
4j
IRON, COBALT,
AND
NICKEL
403
carbon monoxide. At a comparatively low temperature! ferric oxide is converted completely to the magnetic oxide:
2Fe 3 4 + CO 2 At higher temperatures reduced to ferrous oxide, and then to the metal, but these reactions involve measurable equilibria and are reversible, depending upon the relative pressures of carbon
.
3Fe 2 O 3
+ CO =
this oxide is
monoxide and
dioxide.
TABLE
Values for the ratio
III
REACTIONS OF CARBON MONOXIDE AND OXIDES OF IRON
COz/CO
at various temperatures
The modern blast furnace operates so as to carry out these reactions in a continuous manner. The general outline of this furnace is indicated in Fig. 1. The dimensions are
approximately 22 by 90 ft., and the construction is sheet steel lined with difficultly fusible siliceous fire brick. Only ores with low sulfur and phosphorus content are employed, and these may be subjected to a preliminary roasting in order to remove as much sulfur as possible. The ore contains siliceous material, and as all the charge is to be drawn from the furnace in the liquid state, sufficient limestone is added to form an easily fusible calcium silicate slag. Coke is now universally employed as fuel, and is introduced together
with the ore and limestone at the top of the furnace. Dry air, preheated to 425 to 650, is blown in through a number of water jacketed nozzles or tuyeres near the bottom. The air oxidizes the coke in the lower part of the furnace to carbon monoxide (cf. XIII 6). The intense heat of this reaction liquefies the iron which has been reduced in the central part of the furnace by the hot carbon monoxide. From time to time, the molten metal is drawn off, and
404
REFERENCE
[Ch.
XIX
either run into molds, or else conveyed directly to Bessemer converters, or open hearth furnaces, and made into steel.
The crude
iron
is
shape of the casts
made
called cast iron, or "pig iron," from the in the old-fashioned furnaces. The
impurities present depend considerably upon the composition of the ore, the nature of the slag, and the temperature at which the furnace has been maintained. The following
percentages are representative C, 2-4.5 P, 0.-3.0; Mn, 0.2-1. In general, a high temperature of reduction increases the per:
Si,
0.7-3 S, 0. 1-0.3
;
centage of carbon and silicon, but diminishes that of the

sulfur through the reaction:
FeS
+ CaO + CO = Fe + CaS + CO Practically

2.
all of the phosphorus in the charge collects in the iron as
Fe 8 P.
The production
of pig iron
in the United States reached a peak of 57,000,000 tons in
1944.
The melting
is is brittle
point of
pig iron
metal
about 1150. The and suitable
only for castings not subject Hot Air When cooled Blast to shock. rapidly, the carbon remains in combination and the product is called white cast iron; but when cooled slowly, much FlG Blast furnace (diagrammatic) of the carbon separates as graphite and the product, known as grey cast iron, is softer
.
and tougher.
position:
Blast furnace slag has the approximate percentage comSiO 2 , 20-70; CaO and MgO, 25-50; A1 2 O 8 5-20;
,
5]
IRON, COBALT,
AND
NICKEL
405
CaS, 1-4; FeO, 1. In some cases, the composition is suctt that the slag may be ground and made into cement. Large
quantities are also used in paving, in combination with tar. The flue gas contains considerable heat value through its
high carbon monoxide content. Part of the gas is burned in the so-called hot-blast stoves, which are used to preheat the air blast, and the rest is employed to develop power about the plant. The gas is generally cleaned from dust before using for power, and the solid obtained contains appreciable quantities of potassium salts, and constitutes a potential
source of this alkali.
Wrought Iron. Wrought iron is manufactured from by oxidizing out the impurities through melting in a reverberatory furnace with iron oxide and a basic flux. As
6.
pig iron
the iron becomes pure,

collects in
its
melting point
rises,
and the metal
lumps which are removed from the furnace. It possesses a fibrous is soft and malleable. structure due to the inclusion of slag, since the temperature
Wrought
iron
of the process is not high enough to melt the pure iron
and obtain a good separation from the slag. Wrought iron,

1125
while formerly of great importance,

6.
is
now
largely re-
placed by mild
Steel.
steel.
Iron which con-
BOO
123466
2.
6.67
Per cent Carbon (6.67 %C
100% Fe 3C)
FIG.
when quenched is called steel. The properties of steel are greatly influenced by small amounts of carbon, as may be best explained by reference
to the iron-carbon diagram, Fig. 2. If a- molten solution of less than 4.2 per cent of carbon in iron is cooled, the solid which first separates is a solid solution of carbon or iron carbide in 7-iron, called austenite
The
iron-carbon diagram.
from 0.05 to 2.0 per carbon and which is capable of being hardened
tains
cent
406
DEFERENCE
[Ch.
XIX
(The diagram also shows a solution in 5-iron above 1300 but this is somewhat uncertain.) At higher concentrations of carbon, the solid phase which separates is cementite, FeaC. This is metastable in respect to the decomposition into carbon and iron, but the reaction is not rapid. The eutectic of the austenite-cementite phases lies at about 1150. Austenite, containing more than 0.9 per cent carbon,
upon cooling
yields
<*-
yields cementite; if it contains less carbon, it or /8-iron as shown in the diagram. The eutectic
temperature is 690, and the eutectic mixture of a-iron and cementite is known as pearlite. However, if austenite is cooled sufficiently rapidly, these transformations do not occur, and the solid solution may thus be obtained at room temperatures as a tough metal of low magnetic susceptibility.
TABLE
IV
COMPOSITION AND PHYSICAL PROPERTIES OF SIMPLE CARBON STEELS
Various methods of heat treating steel are in use. Thus if supercooled high carbon austenite is heated above 750 C. rapid equilibrium is established and some cementite separates. If the steel is held at this temperature for some time
and cooled slowly the process
is
called annealing;
if
cooled
rapidly, quenching. Tempered steel is held for some time at a temperature below the point at which rapid equilibrium
is
established.
8]
IRON, COBALT,
AND
NICKEL
407
The properties of the heat treated steel are thus greatly affected by the temperature and length of time of the treatment, as this determines the size of the interlacing crystals. The terms martensite and sorbite are applied to intermediate stages of the transformation of austenite into pearlite,
7. Many important special steels are made by the addition of elements other than carbon. The presence of other
elements greatly modifies the temperature of the ironcarbon phase diagram. Silicon is not only highly soluble in 7-iron, but also catalyzes the decomposition of cementite to carbon, thus rendering the steel soft. Nickel forms a complete series of solid solutions with 7-iron, and since the
stable form of nickel
is
the face-centered cubic-lattice like
7-iron, its presence tends to prevent the transformation of the latter into ex-iron. The special high speed tool-steels (Par. 19) which retain their temper at high temperatures
also
owe
their properties, at least in part, to interference
with the change of 7- into a-iron. Phosphorus in steel was formerly considered most undesirable but a number of high phosphorus steels are now important. The use of alloy cast iron has greatly increased in recent years, the principal alloying metals being chromium, nickel,
copper, and
molybdenum. The following are

;
typical
com-
positions: automobile blocks, C, 3.3, Si, 2.2,

0.35, Ni, 0.70, Fe, balance
Mn,
0.75, Cr,
brake drums, C,
3.2, Si, 2.0,
Mn,
0.6, Cu, 1.0, Mo, 0.5, Fe, balance. 8. Manufacture of Steel. The
steel is
American production of about 50 million tons annually. Various manufac-
turing processes are employed, depending upon the impurities present and the type of steel desired. By far the largest percentage (91.5) of the steel manufactured in the United States is made by the open-hearth process. Of the
remaining, 6.8 per cent

furnace.
(a)
is
Bessemer and
1.7 per cent electric
Open-hearth
Steel.
steel industry in the past
The tremendous expansion of the 50 years was rendered possible
408
REFERENCE
[Ch.
XIX
through the development of the basic open-hearth process, whereby high-grade steel may be made from pig iron relatively high in phosphorus and sulfur. The process consists of heating a charge of pig iron and scrap steel with sufficient iron oxide to oxidize the sulfur,
phosphorus, and most of the carbon, in a furnace lined with The carbon monoxide calcined magnesite or dolomite. formed escapes as a gas, while the oxides of sulfur and phos-
phorus combine with the basic oxides to form a slag. The metal is contained in a shallow hearth (about 40 by 1 2 feet and 2 feet deep), and the heat is supplied by a gas flame directly over the surface. As mentioned above, the basic oxides also serve as a lining for the hearth. When the desired carbon content is reached, generally after about 8 hours, the heating is stopped and the melted steel is run into large ladles. Some iron low in sulfur and phosphorus is made into steel by the acid open-hearth process, which is essentially the same as the above, except that the hearth
lining
(b) air is
is silica.
In the Bessemer process, a blast of blown through molten pig iron until the impurities are oxidized. The acid process, in which the furnace is
Bessemer
Steel.
lined with silica, is applicable only to iron low in sulfur and phosphorus as these elements are not readily oxidized under
these conditions.
basic lining is employed in certain which permits the removal of the phosEuropean phorus in the basic slag; however, the iron must be low in
districts,
sulfur.
The Bessemer converter
is
a large egg-shaped vessel
mounted on trunnions so as to turn about its shorter axis. The molten metal is poured in through the necklike opening
in the top, while the converter is in a horizontal position. The air-blast, which enters through perforations in the bot-
then turned on, and the converter raised to an upright position. The heats of combustion of the carbon and silicon keep the metal molten in spite of the higher melting
tom,
is
9]
IRON, COBALT,
AND
NICKEL
409
/
point of the pure iron. The "blow" is finished in about? ten minutes, and the converter is turned on its side so that a calculated quantity of carbon, manganese, or other metals may be added. (c) Crucible and Electrothermal Steel. The finest grades of
have long been made by heating wrought iron with pure carbon in small crucibles, and the product is known as crucible steel. Much of the high-grade steel is made in small electrically heated furnaces. The method is
tool-steel
similar to the open-hearth process, except that the mode of heating permits more careful control. Most of the electric
furnace product is alloy steel. In the manufacture of armor (d) Case-hardened Steel.
plate,
desirable to harden the surface
and many auto and other machine parts, it is often and at the same time keep the toughness of the body of the metal. This is accomplished by heating the article, packed in carbon or in cyanide, until the desired amount of carbon is absorbed into Another form of surface hardening called the surface.
nitriding consists in heating an alloy steel (usually containing Al, Cr, or Mo) in an atmosphere of ammonia. Nitrides
of the alloying metals are thus formed on the surface. 9. Reactions of Iron. Iron is a good reducing agent at
ordinary temperature, and a very powerful reducing agent at high temperature, combining readily with all of the negative elements (Table V). Iron and oxygen do not react in the cold, but when heated
they form ferroferric oxide, Fe 8 O4 and at higher tempera;
tures ferric oxide, Fe 2 O 3
The
equilibria
between
considerable importance;
iron, iron oxides, and steam are of and the ratios of 2 O/H 2 for the
systems, Fe
The
given in Table V. solid phases in these systems appear to be solid solu:

:
,
'
FeO and FeO Fe 3 O4 and
tions.
At lower temperatures the
+ 4H O =
2
FeaO4
+ 4H
2,
reaction is entirely 3Fe as ferrous oxide is unstable in
410
REFERENCE
[Ch.
XIX
TABLE V
CONSTANTS BOR THE IRON AND STEAM EQUILIBRIA
respect to iron and Fe 3 O 4 below
570; and
0.2.
at
400, the
ratio,
O/H 2
in this equilibrium is
about
The equilibria between iron, iron oxides, and the oxides of carbon have been discussed in connection with the blast
furnace, Par. 4. Iron dissolves in dilute acids with the evolution of hydrogen and the formation of ferrous salts. Strong oxidizing
agents yield ferric compounds, but very powerful oxidizing agents, such as concentrated nitric acid or dichromate, render the metal passive and in this condition it is not dis;
reduce cupric solutions. Passivity destroyed by scratching the surface, by the action of reducing agents, or by placing the metal in a powersolved
by
hydrogen ion nor will
it
is
magnetic field. The phenomenon appears to be due to the formation of a surface film of oxide.
ful
Tb^ rusting of iron involves two steps: (1) the oxidation to ferrous ion by acid, usually carbonic, i.e. Fe 4-2H 2 CO 3 - Pe** 2HCO 32 and (2) the formation of ferric oxide (iron rust) by the atmospheric oxygen: 4Fe~
+
3
+ H
+ 8HCO + O +
2
6H 2 O = 2Fe O 3 -H O
2
+ 8H CO
2
3.
step does not take place readily with pure iron, due to the overvoltage effect of hydrogen on the metal.
first
The
the presence of impurities which present surfaces for the escape of the gas. Pure water is about equal to ferrous ion as an oxidizing agent (Ap-
Rusting
is,
therefore, favored
by
pend.
II),
so there
is
not
much driving power to the
solution
of the metal in pure water; the reaction is, of course, favored by increasing the concentration of hydrogen ion.
11]
IRON, COBALT,
AND
VI
NICKEL
41
TABLE
3Fe -f 2O 2 - Fe 8 O 4 Fe + S - FeS 2Fe H- 3X2 = 2FeXj 2Fe -f 2H+ - Fe ++ + H 2 3Fe + C = Fe 3 C Fe + Si = FeSi 3Fe + P = Fe 8 P 3Fe + 4H 2O(stoam) - Fe aO 4 + Fe + 5CO - Fe(CO) 6 Fe + CO 2 = FeO -f CO 4Fe + 2NH 8 = 2Fe 2 N + 3H 2
REACTIONS OF IRON
Readily at 500, Fe 2O 8 at higher temp. Heated Halogens except la which gives Fel*
Reaction potential
+ 0.44
volt
Above 1,200 Also Fe 2 Si
4H 2
See Table V See Par. 15 See Table III Fe does not react directly with
COMPOUNDS OF IRON
10.
Oxidation States.
Iron forms two important series
of salts: ferrous, with an oxidation state of 2, and ferric, with an oxidation state of 3. In addition, salts are known
in which iron has the 6 oxidation of ferrate ion, FeO4 state and there is some evidence for perferrite, FeO 3
,
Oxidation-reduction potentials relating to the oxidation

states are given below
:
VOLTS
Fe - Fe+ + + 2e~ Fe -f- 2OH- = Fe(OH) 2 + 2c~ Fe++ - Fe +++ + tr Fe(OH) 2 + OH- = Fe(OH) 8 + e~ = Fe(CN) 6 + <r Fe(CN) 6 Fe+ + + + 4H 2 O Fe0 4 + 8H + + 3e~ + 4H 2O + 3er Fe(OH) 8 + 5OH- - FeO 4
-f 0.44
+ 0.88
0.77
0.49)
1.9
+ 0.56
<-
<-
(-
0.9
follows from these values that the reaction, Fe ~ 2Fe~H + = SFe"*" ", is practically quantitative. Also ferrous iron is readily oxidized to ferric in alkaline solution,
It
but much less readily in acid; in fact, acid ferrous solutions are oxidized to ferric only very slowly by the air, as the reaction potential is above that of oxygen to hydrogen peroxide (Append. II), which is the first step of the oxygen reThe ferrates are such powerful oxidizing agents action.
that they are difficult to prepare, and very unstable. Ferrous compounds resemble 11. Ferrous Compounds.
manganous
in their solubilities.
The hydroxide, Fe(OH) 2
41*
is
REFERENCE
[Ch.
XIX
is
is
precipitated from ferrous solutions by alkalies, but it only moderately insoluble in water and its solubility
greatly increased in ammonium salts. The pure hydroxide is white, but in the air it quickly turns green, and then reddish-brown through oxidation to ferric hydroxide. The
be prepared by heating the oxalate, but the product contains some iron and ferric oxide. It burns when heated in air. Ferrous ion has a pale green color. Ferrous sulfide forms through the direct union of the It forms as a black precipitate when soluble elements. sulfides are added to neutral or basic ferrous solutions, but
oxide, FeO,
may
readily soluble in acids. The naturally occurring sulfide generally contains an excess of sulfur in solid solution (cf
is
composition
sulfur to
'
Cu
2 S,
VII
8).
Ferrous sulfide combines with

,
form the
It is
'fools'
gold."
disulfide, FeS 2 known as iron pyrites or It occurs in nature as brass-colored cubic
crystals.
decomposed
not dissolved by dilute acids, but is slowly by concentrated hydrochloric acid, FeS 2
2HC1 = FeCl 2
+H
S,
and rapidly by
nitric acid
with the oxidation of the sulfur. An orthorhombic modification called marcasite also occurs. Pyrite is an important source of sulfur for the manufacture of sulfuric acid. Ferrous sulfate, FeSO4 is the most important ferrous salt.. It is prepared commercially by the oxidation of moist
,
pyrites:
2FeS 2
+ 7O + 2H O = 2FeSO + 2H SO
2
2
4.
The
hydrate, FeSO4 *7H 2 O, which crystallizes upon evaporation of the water solution, is known as green vitriol or copperas. It is used as a disinfectant, in the manufacture of dyes, and in the preparation of ink.
The common black or blue inks contain
the ferrous salt of
gallotannic acid. This is not colored, but upon exposure to the air the black ferric salt is precipitated. black or blue
dye gives the initial color of the ink. Ferrous ammonium sulfate, (NH 4 ) 2 Fe(SO4 }2 '6H 2 O, may be crystallized from equimolar solutions of the two sulfates. This salt is very stable toward oxidation by the air, and is
12]
IRON, COBALT,
AND
NICKEL
413
employed as a primary standard 12). (cf. XVIII

Ferrous carbonate,
ferrous solutions
,
in quantitative analysis
by
FeCO 3 is readily precipitated from soluble carbonates. It occurs in nature
as the mineral, siderite. Ferrous halides are readily soluble in water. They may be prepared by various methods, e.g. by dissolving the metal in the halogen acid, or by the action of the halogen
upon excess of the metal.
FeC 2 O4 forms as a yellow precipitate the addition of oxalate to a ferrous solution. With upon excess reagent, it dissolves with the formation of a yellowish red solution containing the complex ion, Fe(C2O4 )2
Ferrous oxalate,
,
Aqueous
solutions of ferrous ion absorb nitric oxide with
the formation of the ferronitroso complex ion, FeNO++. This is the basis of the "ring test" for nitrates (cf. XI 39). The complex ferrous cyanides are discussed in Para-
graph
13.
,
Compounds. Ferric oxide, Fe 2 O 3 and its hydrate, Fe 2 O 3 -H 2 O, are the most important ores of iron. In the various complex minerals containing this oxide, it generally behaves as an acid oxide, its salts being known as ferrites. One of the most common of these compounds is ferrous ferrite or magnetite, Fe 3 O4 i.e. Fe(FeO 2 ) 2 As its common name indicates, it is highly magnetic, and large
12. Ferric
,
specimens are known as "lode stones." Ferrites may be prepared by fusing ferric oxide with basic oxides, e.g. NaFeO 2 Ca(FeO 2 ) 2 and ferrous acid, HFeO 2 (Fe 2 O 3 -H 2 O), is obtained by the action of water upon sodium ferrite.
, ,
The oxide exists in many
modifications.
<*-Fe 2
3,
hematite,
varies in color from yellow to dark red depending upon the state of subdivision. The ferromagnetic, or 7-Fe 2 3 also is yellow to red.
oxide loses oxygen to form magnetite, but at lower temperatures, about 1300, the reaction is O 2 = 6Fe 2 O 3 slowly reversed: 4Fe 8 O 4
ferric
Around 3000
414
REFERENCE
[Ch.
XIX
Finely divided ferric oxide under the names "rouge" and "Venetian red," is used as an abrasive and as a pigment. Four forms of precipitated ferric oxide, so-called ferric hydroxide, are known. The addition of alkali to ferric solutions precipitates the brown gel which is hydrous a-Fe 2 O3. The slow hydrolysis of most ferric salts yields -Fe 2 O3-H 2 O which dehydrates to a-Fe 2 Os. The hydrolysis of ferric chloride forms /3-Fe 2 O 3 *H 2 O. This also gives a-Fe 2 O 3 upon
The oxidation of ferrous compounds and dehydration. solutions with certain oxidizing agents forms 7-Fe 2 O 3 2O which gives 7-Fe 2 O 3 on dehydration. Ferric oxide sols are
remarkably stable. They are ordinarily positively charged and may be coagulated by negative ions, but if the negative
strongly adsorbed, a reversal of the sign of the charge occur with the formation of a negative sol. may Ferric oxide is a weak base, and in water solution shows but slightly the acid properties exhibited by the oxide in its mineral compounds, in that it is not soluble in excess of dilute alkali, and only slightly in concentrated alkali. Due to the weak basic properties of ferric hydroxide,
ion
is
ferric salts are highly hydrolyzed, and their characteristic yellow brown color in solution appears to be due to the
colloidal
hydroxide or to basic ions.
When
this is repressed
by
acid, the yellow color
becomes
lighter.
Ferric halides, except the iodide, may be prepared by the action of the halogen upon the metal, or by dissolving the hydroxide in acid. Iodide ion is oxidized by ferric ion:
2Fe +++
.
21"
= 2Fe ++
I 2,
but the reaction
is
not com-
plete unless the equilibrium is displaced by the removal of The halides are very soluble, forming many hythe I 2 drates. With excess of halide ion, they form complex hal-
ides;
and many of the complex

.
salts are
known,
e.g.
KsFeF 6
and
(NH 4 )3FeCl6
Magnetic data indicate that these complex ions are ionic in character and not covalent as, for example, are the com-
12]
IRON, COBALT,
is
AND
NICKEL
415
plex cyanides. The fluoride does not oxidize iodide.
quite stable and in solution
Hydrogen
sulfide in acid solution reduces ferric salts to

if
ferrous with the precipitation of sulfur, but

sulfide is used, ferric sulfide,
ammonium
The
Fe 2 S 3
is
precipitated.
pure compound is unstable, but ferric sulfide complexes with other metallic sulfides occur in nature.
Ferric sulfate, Fe 2 (S0 4 ) 3 and ferric nitrate, Fe(NO 3 ) 3 are both soluble, but tend to form basic salts by hydrolysis. 3 ions, forms alums, The former, like most sulfates of
,
e.g.
KFe(SO
4) 2
-12H 2 O.
Ferric phosphate,
FePO 4
is
common
constituent of
phosphate rock. It is very slightly soluble, and may be precipitated from an acetic acid solution of ferric ion. It is,
however, soluble in strong acids.
Ferric ion, like the ferrous, also forms a complex oxalate which accounts for the use of oxalic acid ion, Fe(C 2 O 4 )3
,
in
removing ink and iron rust spots from fabrics. The soluble red thiocyanate Fe(SCN) 3 forms the complex ion, ~3 with excess of thiocyanate. Fe(SCN) 6
,
Complex Iron Cyanides. Both ferrous and ferric ion form complex ions with excess cyanide, the former yielding ~4 and the latter ferricyanide, ferrocyanide, Fe(CN) 6 ~3 These complex ions are so stable that their Fe(CN) 6 solutions show virtually none of the properties of the iron
13.
,
or cyanide ions. The structure of these ions is octohedral, which is the general structure of covalent complexes which involve two d, one s, and three p orbitals of the central atom.
Sodium and potassium ferrocyanide, Na4 Fe(CN) 6 -10H 2 O, and K4 Fe(CN) 6 '3H 2 O, are usually prepared as by-products
from the
distillation of coal.
A considerable
portion of the
nitrogen in coal is liberated as hydrogen cyanide, This is absorbed in iron oxide purifiers as iron cyanide,
HCN.
which
then treated with lime to form calcium ferrocyanide; this, in turn, is converted into the alkali ferrocyanide. Formerlv, the ferrocvanides were prepared by fusing nitrogis
416
REFERENCE
[Ch.
XIX
enous material with potash and iron turnings. The potassium compound is commonly called "yellow prussiate of potash." The hydrates decompose at about 100, yielding colorless powders which ignite when heated in air. With
lyzed,
concentrated sulfuric acid the cyanide ion is slowly hydroforming ammonium ion and carbon monoxide:
K4Fe(CN) 6
4
+ 6H SO4 + 6H O = 2K SO4 + FeSO4 SO + 6CO. When heated with metallic sodium, + 3(NH ) 2
2
the iron is reduced and a mixture of metallic iron and alkali cyanide formed. With hydrochloric acid, the weak hydroferrocyanic acid, H 4 Fe(CN) 6 is formed. This acid may be extracted from concentrated water solution by ether, from which it crystallizes as a colorless compound, stable in dry air, but readily oxidized in moist air.
,
ferrocyanide-ferricyanide couple possesses moderately strong oxidizing power. The value of the potential given in Par. 10 is for equal concentration of the two ions
The
and is not corrected for the activities, the E value is around 0.36. Ferrocyanides are readily converted into
ferricyanides
by the action
of chlorine in solution.
The
commercial preparation of potassium ferricyanide or "red prussiate of potash," K 3 Fe(CN) 6 depends upon this oxidation. The ferricyanide ion is not as stable as the ferrous
,
sium ferrous-ferrocyanide, K 2 Fe[Fe(CN) 6 ]. A number of the ferrocyanides are important in analytical chemistry, especially the compounds with zinc and uranium, Zn 3 K 2 [Fe(CN) 6 2 and K,UO,[Fe(CN)J. Ferricyanide yields with ferric ion a deep brown solution, probably of undissociated ferric ferricyanide. With ferrous
]
complex, and decomposes slowly in the sunlight. Alkali ferrocyanides form with ferric ion, first a soluble blue compound, KFe 2 (CN) 6 called potassium berlinate or soluble Prussian blue, and then a very slightly soluble precipitate of Prussian blue, Fe 7 Ci 8 Ni 8 -10H 2 O, (vide infra), which is an important blue pigment. With ferrous ion, potassium ferrocyanide forms a white precipitate of potas,
14]
IRON, COBALT,
AND
NICKEL
417
ion a precipitate, TurnbuH's blue, is formed. From X-ray analysis the structure of solid ferric ferricyanide has been determined as a cubic sodium chloride lattice. Each ferri-
cyanide ion is thus surrounded by six ferric ions and the cyanide ion serves as a bond between the iron ions, FeCNFe. The structure of potassium berlinate is similar except that + in the center. The relaalternate small cubes contain a
tion of the iron
and cyanide
is
2
also the
same
sium
ferrous- ferrocyanide,
FeFe(CN)e,
in the potasbut in this case
each small cube is occupied by a 4 Prussian blue appears to be ferric berlinate Fe[FeFe(CN) 6 ]3 and the TurnbuH's
".
blue ferrous berlinate, Fe[FeFe(CN) 6 ]2. The linkage between the berlinate ions in the solid is probably of the same
type as that found for FeFe(CN) 6 A number of copper ferrocyanides are known which are probably derivatives of
.
2 supercomplexes, e.g., Cu[CuFe(CN) 6 ], and [CuFe(CN) 6 ]. Zinc, however, appears to be unable to coordinate with six cyanides and the supercomplex structure
similar
is
more complicated,
Blue print paper
is
e.g.
[Zn 3 [Fe(CN) 6 ] 2 ]"~
2
.
made by treating paper with a solution
of ammonium When exposed
ferricyanide and ferric citrate in the dark. to light, reduction of the iron by the citrate
takes place with the formation of Prussian blue. The print is fixed by washing out the unchanged mixture with water. One of the cyanide groups, in either the ferro- or ferricyanide,
may
2 ~,
SO
NO
be replaced by other groups; e.g. NO, CO, 2 O, 3 AsO 2 -, forming complex pentacy-
NH
anides.
Sodium f erri-nitrosopentacyanide, Na 2 FeNO(CN) 6
O, gives an intense blue color with sulfide in alkaline solutions, thus constituting a delicate test for the latter substance. Barium and strontium 14. Perferrites and Ferrates.
2
2H
BaFeO 3 and SrFeO 3 have been prepared by mixtures of the hydroxide with ferric hydroxide in heating a current of oxygen. The compounds are decomposed by water, and there is but slight evidence for the formation of
perferrites,
, ,
418
REFERENCE
[Ch.
XIX
the dioxide of iron. The ferryl ion, FeO ++, may possibly exist at low concentrations under some conditions.
Powerful oxidizing agents in fused alkali or in very conalkaline solution oxidize ferric hydroxide to ferrate. Barium ferrate, BaFeO4 analogous to the sulfate, is but slightly soluble and is the most stable of the ferrates. It is not decomposed by water or cold dilute sulcentrated
,
furic acid; but with cold hydrochloric acid, chlorine and oxygen are evolved, though the solution first assumes the
red color characteristic of

15.
FeO4
Iron Carbonyls. Finely divided iron reacts slowly with carbon monoxide to form the pentacarbonyl, Fe(CO) 5 which may be distilled off by heating to 120. This sub,
stance freezes at 21, boils at 102, and decomposes when above 200. In the sunlight it decomposes: 2Fe(CO) 5 heated
= Fe 2 (CO)9
upon
CO.
heating to form
2
This latter compound decomposes Fe 3 (CO)i 2 The pentacarbonyl dis.
solves in alkalies:
Fe(CO) + 4OH~ = Fe(CO)

6
~ + CO
+ 2H
O.
Fe(CO) 4 H 2 is properties and forms many

,
Upon
acidifying in the cold the carbonyl hydride, liberated. This carbonyl hydride has acid
salts.
When
,
oxidized with hy-
drogen peroxide it forms Fe 3 (CO)i 2 and when warmed it decomposes: 2Fe(CO) 4 H 2 = Fe(CO) 5 + Fe(CO) 3 (polymerThe mercuric salt is prepared by oxidizing ized) + 2H 2 the pentacarbonyl with mercuric chloride: Fe(CO) 5 + H 2 O
.
HgCl 2 = Fe(CO) 4 Hg
2HC1
+ CO
2.
The
structure of
Fe 2 (CO) 9 appears to be (CO) 3 Fe

be noted that in
the same
all
\CO/
X)C\ CO Fe(CO)
3.
It
may
compounds the iron atom has (if the two shared with each CO is included) as has the next inert gas krypton. The same is true of the nitrosyl carbonyl Fe(CO) 2 (NO) 2 if one assumes that the odd electron on the nitric oxide has transof these
number
of electrons
ferred to the iron.
16]
IRON, COBALT,
AND
NICKEL
419
16. Analytical.
The formation
of Prussian blue, through
the reaction of ferrocyanide with ferric ion, and ferricyanide with ferrous ion, serve to identify iron in both of the common valence states. Ferric iron may be distinguished also by the deep red color of ferrisulfocyanide, Fe(SCN) 3 and a
,
bright red compound with pyrocatechol. In the scheme for the systematic separation of the elements, iron salts are precipitated by ammonium sulfide
and hydroxide as ferrous sulfide. The general method of separation from the other members of this analytical group is indicated in Appendix VI. In case phosphate is present,
the analytical procedure requires some modification, because ammonium hydroxide will precipitate ferric phosphate
from
ferric solutions.
so-called basic acetate separation, which is often used in the iron group, is carried out by the addition of ammonium acetate to a slightly acid solution. Upon heating, hydrolysis occurs; and the precipitate may contain Fe,
The
Ga, Cr, V,
is
W,
Al, In, Zr, Ti, as hydroxides, basic acetates,

(if
phosphates, or vanadates, and the rare earths

present).
phosphate
serves to separate these elements from Mn, Zn, Co, Ni, U, alkaline earths, and rare earths (if phosphate is not present), although traces of Zn, Co,
The method
and may be present in the precipitate. In gravimetric analysis, iron is usually precipitated as ferric hydroxide by ammonium hydroxide and weighed as
Ni, Be,
ferric oxide.
is
reagent, "cupferron," C 6 5 N-NOONH4, sometimes used to precipitate iron as the ferric salt. This
The
method has the advantage of precipitating iron (and also Cu, Ti, and Zr) from highly acid solutions, and thus effectWhen ing a separation from Al, Cr, Mn, Ni, and Co.
ammonium hydroxide, the precipitate is to ferric hydroxide. changed Iron is determined in volumetric analysis usually by one 8H+ = Mn++ of the two reactions: 5Fe++ 4
treated
with
4-
5Fe+++
+ 4H O,
2
and 6Fe++
+ MnO +
Cr2 O 7
14H+
420
REFERENCE
[Ch.
XIX
In the dichromate method determined by removing a drop of the solution and testing with ferricyanide, or by the addition of an oxidation indicator, e.g., diphenylamine which gives a blue
= 6Fe+++ + 2Cr+++ + 7H 2 O.
is
the end-point
color
upon oxidation.
In the permanganate
method the
color of the reagent serves as
an end-point indicator. The
dichromate method is readily applicable in the presence of chloride, but permanganate tends to evolve chlorine under these conditions, unless an excess of manganous ion is added (cf. XVIII 12).
In the preparation of the ferrous solution before titration, ferric iron may be reduced in various ways, but the most
generally employed methods are: (1) reduction by passing the solution through a tube containing zinc amalgam (Jones reductor), (2) reduction with stannous chloride followed by
removal of excess stannous ion by mercuric chloride.

Ferric salts in solution may also be titrated directly with titanous chloride, using thiocyanate as an indicator:
COBALT AND NICKEL

Occurrence. The iron meteors contain about six per cent of nickel, and it seems probable that this percentage also exists in the central core of the earth. However, in the igneous rocks on the earth's crust, the estimated 5 percentage of nickel is 0.020 and cobalt 1 X 10~ The commonest cobalt minerals are: smaltite, CoAs$;
17.
.
cobaltite,
CoAsS; erythrite, Co3(AsO4 )'8H 2 O; and linnaeite, These ores are generally associated with iron, and often nickel, copper, and silver. The principal source of
Co 3S4
cobalt
is
the rich silver-cobalt-nickel veins in Ontario,

nickel ores are: pentalandite,
Canada.
The two most important

NiS-2FeS, and
deposits of
Mg]SiO 3 -nH 2 O. Extensive the former mixed with iron and copper sulfide
garnierite, [Ni,
18]
IRON, COBALT,
AND
NICKEL
421
are found in Ontario, Canada, and of the latter in New Caledonia. Nickel also occurs in other complex sul fides, silicates, arsenides, arsenates, tellurides, oxides, and sulfates. Copper ores usually contain small amounts of nickel, which are removed in the electrolytic refining process.
18.
tario
is
Metallurgy. The cobalt-silver arsenide ore of Onsmelted with a suitable flux in a small blast furnace,
yielding crude silver bullion, and a speiss of the arsenides of cobalt, nickel, iron, copper, and some silver. This speiss is subjected to successive roasting processes; with silica to re-
sodium nitrate and carbonate to form sodium arsenate and with salt to form chlorides of cobalt, nickel, copper, and silver. The soluble chloride is extracted
iron; with
;
move
with water; the copper precipitated as the metal by reduction,
nickel precipitated as hydroxides. The separation of cobalt and nickel is effected by the Mond process (see below), or by the formation of potassium
and the cobalt and
cobaltinitrite (Par. 24), or chloropentammine cobaltichloride (Par. 24). The metal is made by reducing the oxide
with carbon.
The metallurgy
of nickel ores
is
somewhat
is is
similar.
The
product of the blast furnace smelting copper, and nickel sulfides. This matte
of the iron
silicate slag.
a matte of iron,
freed
from much
by
oxidizing in a Bessemer converter with a
In the Orford process, the Bessemer matte is fused with carbon and sodium sulfate, which effects a separation of
rather pure nickel sulfide in the bottom layer. This sulfide is roasted to the oxide, and reduced by carbon to the metal. In the Mond process, the matte is roasted to the oxide, reduced to the metal by water gas at 300, and the nickel
removed by
volatilization as the carbonyl,
Ni(CO) 4
in
stream of carbon monoxide at a temperature of 50 to 100. The carbonyl is then decomposed into the metal and carbon monoxide by heating. Electrolytic refinement of nickel is also employed. The
422
REFERENCE
[Ch.
XIX
is made the anode in a cell using nickel sulfate The pure metal is precipitated on an aluminum electrolyte. cathode. The platinum metals precipitate in the anode mud
impure metal
and the base metals remain
in the electrolyte.
The important atomic and physical 19. The Metals. constants of the metals are given in Table VII. Unlike iron, cobalt and nickel do not have at low temperatures a body
centered cubic type of crystal lattice, but are face centered. They do, however, process magnetic transitions similar to iron and the non-magnetic forms are isomorphous with the face centered, or 7-iron. The metals are silver-grey in color,
;
malleable, and ductile.
TABLE
VII
ATOMIC AND PHYSICAL PROPERTIES OF COBALT AND NICKEL
rapidly developing very extensive industrial applications. Its most important use is as a constituent of the group of alloys known as stellite, which contain cobalt and one or more of the metals chromium, tungsten, molybis
Cobalt
denum, iron, and nickel. Representative composition of two such alloys are: (1) Co 60, Cr 15, 20, Mo 5, and 14, Cr 4. These alloys are used as cut(2) Co 30, Fe 52, ting tools in high-speed lathes, as they do not lose their edge with heating; and also as surgical instruments, since they
may
be
sterilized in
a flame without injury to the edge or
19]
IRON, COBALT,
AND
NICKEL
423
polish. Cobalt alloys for permanent magnets have extensive use in electrical fields. Typical alloys are: alnico II,
Co
Fe
12.5,
Al 10, Ni
17,
38.5; hyperco,
its
Co
Fe 60.5; vicalloy, Co 52, Alnico can 35, Cr 1, Fe 64.

Cobalt-thorium
9.5,
lift
60
are
times
own
in the
weight.
catalysts
Fischer-Tropsch production of gasoline. The electrolytic nickel plating industry is one of the largest consumers of nickel. The plated coat is hard, suscep-
employed
tible of
high polishing, and
is
electrolyte generally
employed
resistant to tarnishing. The is nickel ammonium sulfate.
Finely divided or "active" nickel, prepared by reducing the oxide below 300, is employed as a catalyst in a number of hydrogenation reactions; the most important commercially being the
hardening of fats and
oils
by
their
tion with hydrogen, and the conversion of carbon and steam into carbon dioxide and hydrogen.
combinamonoxide
TABLE
VIII
NICKEL ALLOYS
Nickel forms an unusually large number of alloys of technical importance (Table VIII). Approximately half of the 160 million pounds of the metal consumed annually
424
in the
REFERENCE
[Ch.
XIX
United States went into nickel steel into nonferrous alloys.
and 40 per cent
20, Reactions of the Metals. The difficulty of oxidation increases gradually in going from iron to cobalt and nickel (see Par. 21 and Par. 27 for potential values), but in general
the reactions of the three metals are similar. Like iron, they are rendered passive by very powerful oxidizing agents. The principal reactions are summarized in Table IX.
TABLE IX
REACTIONS OF COBALT AND NICKEL
+ 2O - Co O 2Ni + O - 2NiO M + 2H+ - M++ + H M + H O -- MO H 3M + 2NO + 8H+ - 3M++ H- 2 NO -h 4H O M + X - MX 4M + 2NH - M N + 3H

3Co
2
8
-|-
Slow at 25. Cf. Pars. 21 and 27 Slow at red heat

Passive with concentrated acid
With
halogens.
Co
also forms
CoF 8
3M
-f
400 to 600
Carbides stable only at temperatures of the molten metals Below 100 but with Co only under
pressure
M + 4CO
M +S
21.
= M(CO) 4
2M + Si -
M Si
2
Co
= MS
also forms CoSi, CoSi 2 and CoSis, and Ni forms NiSi and NisSi2
,
COMPOUNDS OF COBALT
Cobalt, like iron, forms cobaltous, cobaltic, CO+++, ions and compounds, and a few cobaltites, derivatives of the dioxide, CoO 2 which, unlike the corresponding iron oxide, has been prepared. The
Oxidation States.
Co++, and
a very powerful oxidizing agent, and for this compounds are not very stable, except those complexes which give a very small concentration of the metal ion. Potential values are summarized below:
cobaltic ion
is
reason
its
Co m Co++ + 2e~ Co++ - Co+++ + eCo + 20H- - Co(OH) 2 + 2e~ Co(OH) 2 -f OH- * Co(OH) 8 + Co(OH) 8 + OH- - CoO 2 + 2H 2O
Co(CN)<r - Co(CN)(T
4
VOLTS
1
26
+ 0.277 - 84 + 0^42 + e~
ca.
+ e~
1.2
21]
IRON, COBALT,
AND
NICKEL
425
22. Cobaltous Compounds. Cobaltous oxide, CoO, may be prepared by the reduction of the higher oxides with hydrogen. When heated in air, it forms the Cobaltous coThe rose-colored hydroxide Co(OH) 2 baltic oxide, Co 3 O 4 is precipitated when alkali hydroxides are added to cobaltous solutions but darkens in the air through oxidation to
.
cobaltic hydroxide. With concentrated ammonia the hy"" droxide dissolves to form Co(NH 3 ) 6 +4", with excess of Co"
1
1
a green or blue modification of Co(OH) 2
is
precipitated
by
hydroxide. Cobaltous halides are readily formed by dissolving the hydroxide in the halogen acid. They are soluble and form
a number of hydrates. The chloride is sometimes used as a "sympathetic ink," by writing with a solution of the pale pink hexahydrate; the characters are invisible but appear upon warming the paper, due to the formation of the blue
4 is pink anhydrous salt. The color of the ion Co(H 2 O) 6 blue. It has been and that of the complex chloride CoCl 4 suggested that upon dehydration, the hexahydrate, Co(H 2 O)6C1 2 forms the complex salt Co(CoCl 4 ). The sulfate and nitrate are soluble and highly hydrated, and the latter readily decomposes to the sesquioxide upon
1
""
heating.
solution.
Cobaltous sulfide is precipitated by sulfide ion in alkaline Like nickel sulfide, it is unusual in that it is not precipitated from acid solutions, but is not soluble, or only
very slowly so, in dilute hydrochloric acid. Sodium bicarbonate precipitates cobaltous carbonate, CoCO 3 '6H 2O, at room temperature, and the anhydrous compound at higher temperatures. Basic carbonates are
formed by the alkali carbonates. Cobaltous cyanide, Co(CN) 2 *3H 2 O, is but slightly soluble in water, but 'dissolves in excess of cyanide ion to form a
complex cobaltocyanide
ion,
4 CoCCNJe- which, however,

,
is
readily oxidized to the cobaltic complex.
Cobaltous oxide forms important pigments upon fusion
426
REFERENCE
[Ch.
XIX
with certain negative oxides. Smalt, a deep blue pigment, is really a cobalt glass. Cobalt blue is largely cobalt aluminate with more or less zincate. Cobalt green is cobalt zincate, and turquoise green the same with some chromite.
to the powerful oxidizing nature of cobaltic ion (Par. 21), its simple salts are difficult to prepare. The fluoride, CoF 3 forms when the metal is
23. Cobaltic
Compounds.
Due
,
heated with fluorine, and the sulfate, Co 2 (SO4 ) 3 *18H 2 O, may be prepared by the electrolysis of cobaltous sulfate, followed by fractional crystallization. The sulfate forms alums.
These, as well as the simple sulfate, are blue in color. Solutions of the fluoride and sulfate readily hydrolyze to the
hydroxide, Co(OH) 3 (probably hydrous cobaltic oxide), which, when ignited in air, forms Co 3 O4 The cobaltic ion 24. Complex Cobaltic Compounds. forms a remarkable number of complex ions in which it possesses a coordination number of six. These complex ions
.
are
more
is
reason
stable than the corresponding cobaltous ions. The indicated by the following scheme which shows the
number
of electrons in the various orbitals:
3d
4s
4p
5s
Co(CN) 6
-4
OCTAHEDRAL BOND ORBITALS
Thus Co(CN) 6 ~~4 has one
electron in a higher s orbital, and ~3 this electron is readily lost to form Co(CN) 6 The formulae of the more important complexes with
.
ammonia, halides, nitrite, and cyanide are given in Table X and a few of the more familiar compounds are discussed
below:
,
Chloropentammine cobaltichloride, Co(NH 3 ) 6 ClCl 2 forms
when an ammonical solution of cobaltous chloride is oxidized by air or hydrogen peroxide. As it is but slightly
soluble in concentrated hydrochloric acid, the dark reddish-
24]
IRON, COBALT,
AND
NICKEL
427
violet
compound
is
addition of this acid.

of the
precipitated from the solution by the The formation of this compound may
be used to separate cobalt from nickel. The great stability
complex
is
indicated
not removed by acid.

precipitated by silver tact with silver oxide
;
by the fact that the ammonia is Only two thirds of the chloride is nitrate, but upon standing in conit is
converted into the hydroxide,
[Co(NH 3 )5H 2 O](OH) 3 and when

drochloric
acid,
this is dissolved in hythe aquapentammine cobaltichloride, [Co(NH3)6H2O]Cl3, is formed. This compound is not readily
soluble in cold water.
When the chloropentammine is heated

ammonia, the
separates as
under
slight
pressure with concentrated

cobaltichloride,
cobaltinitrite,
2) 6 ,
hexammine
Potassium
tate,
3
[Co(NH
3 )6]Cl 3 ,
orange-colored crystals.
K Co(NO
with potassium
or potassium hexanitrocobalprepared by treating a cobaltous salt nitrite and acetic acid: Co ++ + 3K+
is
2
3
+ 5NOr + 2HNO = K Co(N0
2) 6
+ NO + H
O.
The
potassium salt is but slightly soluble, and is sometimes emThe more soluble ployed as a pigment, cobalt yellow. sodium salt is employed as a reagent in testing for potassium (cf. IV 25). The complex nitrite ion is decomposed
by alkalies, forming the hydroxides, and by strong acids with the liberation of oxides of nitrogen. A number of dinitrotetrammine cobaltic salts have been
NO,
I
NH,
NH
V
I
NK *
/
NH<
/
I
NiV-j-yNO,
prepared. These com^ ,.,. j pounds exhibit isomensm, due to the two possible
.
4 H>
NOjr
NH./
/NO,
arrangements of the coordination groups. _, Cobaltous ion

, ,
.
NH.
in
the
presence of cyanide is readily oxidized, even by hydroThis gen ion to form the cobalticyanide, Co(CN) 6 ion is very stable, and like the corresponding ferricyanide, forms precipitates with ions of many of the heavier
.
metals.
428
REFERENCE

TABLE X
[Ch.
XIX
COBALTIC COORDINATION COMPOUNDS
+3
Cation
Undissociated compounds
[Co(NH 8 ) 6 ]X 8 [Co(NH 8 )5H 2O]X8 [Co(NH 8 ) 4 (H 20) 2 ]X 8

4-
[Co(NH 8 )3(N0 2 ) 8
1
Anion
K[Co(NH 8) 2 (N0 2 ) 4
2
2 Cation
Anion
[Co(NH 8 ) 6 C1]X 2 [Co(NH 8 ) 6 NO 2 ]X 2 [Co(NH 8 ) 4 H 2O, Cl]Xi

4- I Cation
[Co(NH 8 ) (NO 2) ,]
2
3 Anion
K [Co(NO )] K [Co(CN)
8
3
6]
[Co(NH 8 ) 4 Cl 2 ]X [Co(NH 8)4Br 2]X [Co(NH 8 ) 4 (N0 2 ) 2 ]X [Co(NH 8 )4C0 8 ]X
Nomenclature of Complex Compounds. The following system of nomenclature has been proposed by Werner and is in general use
25.
:
the complex is a negative ion, the name of the ion is first. positive (&) In giving the structure of the coordination com(a)
If
plex, the following order is followed (1) Acid radical: Cl~, chloro;
CO
carbonate;
CNS~, thiocyanato; NO 2 ~, nitro, etc. (2) The water or oxygen groups: H 2 O, aqua; O oxo; O 2 peroxo; OH", hydroxo. The ammonia groups. Mono, di, tri, etc. (3) ammine, also called ammino.
,
(4) Name of positive element. If complex is a positive ion, the following endings are used: charge 1, a;
comcharge + 3, i; charge + plex is a negative ion, the termination, ate, is added. (c) If the complex is a positive ion, the acid radicals not in the coordination group complete the name.
charge
2, o;
4, e.
If
Examples:
K [Co(NH
3
[Co(NH 3 )fiCl]Cl 2
3) 2
Chloropentammine cobaltichloride Potassium tetranitrodiammine (NO

2 )4]
cobaltate.
28]
IRON, COBALT,
AND
NICKEL
429
Powerful oxidizing 26. Cobalt Dioxide and Cobaltites. agents in alkaline solution, e.g. hypochlorite and hypoioThe sesquioxide, which is dite, form the dioxide, CoO 2 cobaltous nitrate, is generally conprepared by igniting sidered to be the cobaltous cobaltite, Co(CoO 3 ), as is also the tricobalt tetroxide, Co 3 O 4 i.e., 2CoOCoO2. Other cobaltites have been prepared by fusing cobaltous oxide with
. ,
basic oxides in
air, e.g.,
MgCoO
3.
NICKEL COMPOUNDS
27.
Oxidation States.
is
nickel
2.
No +
The principal oxidation state of 3 hy3 salts are known, and the
droxide which is frequently mentioned in the literature appears to be the dioxide. The dioxide is slightly acidic, and a few salts of it have been prepared. There is some evidence
Both the and + 1 complex cyanides are brown, K 4 Ni(CN) 4 and K 3 Ni(CN) 4 A few nickelates, i.e. K 2 NiO4, have been prepared. Potential values'are summarized below:
for the formation of a
1
oxide.
VOLTS 250
Ni - Ni++ + 2e~ ..................................... Ni++ + 2H 2 = NiO 2 + 4H+ + 2e~ .................... Ni + 2OH- = Ni(OH) 2 -f 2e~ ....................... Ni + 6NH 3 (aq) = Ni(NHi). ++ + 2e~ ...................
+ 0.2S
1.75
+ 0.66
0.48
Ni(OH) 2
4H O = NiO 4
2
+ 2OH-
= NiO 2
+ 2H O + 2e~ ............... - 0.49 + 8H+ + 4<r .................. -1.8

2
Nickelous Compounds. Nickelous compounds are generally green or blue in color, and show many resem28.
blances to cupric compounds. The hydroxide, Ni(OH) 2 forms as a light green precipitate upon the addition of alkalies to a nickel solution. It is soluble in ammonium hy,
droxide, due to the formation of the complex nickel ammonia ion Ni(NH 3 ) 6 f+ which, like the corresponding cupric ion, has a deep blue color. The oxide, NiO, results from the
"
direct Union of the elements, or from the ignition of the hydroxide or the dioxide. The oxide and hydroxide are
readily soluble in acids.
430
REFERENCE
[Ch.
XIX
The halides are readily soluble, highly hydrated in water, and ammonated in liquid ammonia solutions. The bromide, NiBr 2 '6NH 3 is precipitated by the addition of concentrated ammonia to a hot solution of nickel bromide. This property
,
is
sometimes
The
utilized in the separation of nickel from cobalt. cyanide, Ni(CN) 2 is but slightly soluble in water, but
,
dissolves in excess of cyanide, forming the complex cyanide It differs from the ferrous and cobaltous ion, Ni(CN) 4
.
complex cyanides in that it cannot be oxidized to a nickelic and + 1 comcompound, but it may be reduced to the ~ ~4 and Ni(CN) 4 3 The diamagnetic tetra4 plex, Ni(CN) coordinated complexes of Ni^4 (d s p* orbitals) are planar and not tetrahedral. The complex cyanide is an example.
.
"
OS
I
Y\/Y
Ni
|
SO
/\//\C SO OS \/\
C
The
true
l
++ ++ (s p* orbitals). Ni(H 2 O) 4 and Ni(N 2 H 4 ) 2 Below 31, the sulfate crystallyzes as the heptahydrate, NiSO4 '7H 2 O. At higher temperature, two forms of hexahydrated salts are formed, one blue and the other green.
Nickel
nickel
2 4
2
carbonyl, Ni(CO) 4 is tetrahedral and the same is of the paramagnetic complex ions of Ni ++ e.g.,
,
ammonium sulfate, (NH 4 ) Ni(SO ) 6H O, is used in electroplating. The nitrate, Ni(NO 3 )2'6H O, is ex2 2
Alkali carbonates precipitate tremely soluble in water. nickel from solution as a basic carbonate, but the normal carbonate, NiCO 8 *6H 2 O, may be precipitated from a solution containing an excess of carbonic acid. Nickel sulfide, NiS, like cobalt sulfide, is not precipitated from acid solutions by hydrogen sulfide, but is predipitated from ammonia solutions, and the sulfide so formed does not dissolve in dilute hydrochloric acid. The sulfide appears
30]
IRON, COBALT,
AND
NICKEL
431
to exist in three modifications.
The most
soluble modifica-
tion, which is first formed from alkaline solutions, quickly changes to a form which is less soluble, and also less rapidly
Moderately strong oxidizing agents (Par. 27) in alkaline solution convert nickelous oxide into a hydrous oxide which may be a solid
solution of
soluble, in acid. 29. Nickel Dioxide
and
Nickelites.
NiO and NiO 2
With long oxidation the com.
This oxide is position appears to approach that of NiO 2 an extremely powerful oxidizing agent in acid solution, and Barium readily evolves oxygen under these conditions.
nickelite,
BaNi 2 O 5 has been prepared by

,
fusing the oxide
with barium carbonate. Alkali peroxides form with nickelous salts an oxide of the same general formula as the dioxide, but its reactions indicate that it is the nickelous peroxide of
2 nickel.
Hydrous
Edison
nickel dioxide is the oxidizing constituent of the storage battery. The cell reaction upon discharge
may be represented by = Fe(OH) + Ni(OH)

2
the equation: Fe NiO 2 + 2H 2 O The electrodes are iron and nickel 2
dioxide, and the electrolyte, potassium hydroxide. The potential of the cell is about 1.35 volts at 20, and depends but
slightly
upon the concentration
of hydroxide, since this sub-
stance enters into the cell reaction only so far as it affects similar battery employing the activity of the water.
cadmium
instead of iron
1.2 volts.
is
in use in
Europe. This
cell
has
a potential of
In the systematic scheme for separation 30. Analytical. of the positive ions (Append. VI), cobalt and nickel are precipitated as sulfides by ammonium sulfide. In the separation from other
vantage
is
of this analytical group, adtaken of the slow solubility of the sulfides in cold
members
dilute hydrochloric acid and the non-amphoteric character number of procedures are employed of the hydroxides.
in separating cobalt and nickel the simplest probably being the precipitation of nickel by dimethylglyoxime,
;
HON
432
REFERENCE
[Ch.
XIX
C(CH 3 )C(CH
3)
NOH,
as
NKCJÔiNaJj from
solutions
containing acetate and acetic acid. Other methods of separation depend upon the slight solubility of nickel chloride
in
version of cobalt into
an ether-hydrogen chloride solution and upon the conits + 3 compounds, e.g. the precipitation of cobalt as potassium cobaltinitrite; the precipitation of the sesquioxide, Co 2 O 3 by bromine in neutral solution; and the formation of chloropentammine cobalti,
chloride.
In gravimetric analysis nickel
may
be weighed as the
nickel dimethylglyoxime, after drying at 120; as the oxide, NiO; or as the metal after electrolytic precipitation. The
electrolytic precipitation is made from an ammoniacal solution, and nickel and cobalt are deposited together.
Cobalt
is
often precipitated as potassium cobaltinitrite,

salt of nitroso-beta-naphtol,
it is
and as the
Co(Ci
ONO)8o
weighed as the oxide, CoaCX. 31. A comparison of the potential diagrams of iron, cobalt, and nickel with those' ~bf the platinum metals is given in Chapter XX 36.
In both procedures,
Chapter
XX
PLATINUM AND PALLADIUM METALS

rhodium, palladium; and osbear the same relation to the mium, iridium, platinum, second and third transition series that iron, cobalt, and nickel do to the first (cf. XIX). The six elements of these two series are so similar in properties that the separation of the naturally occurring alloys into the pure metals is not simple, and the commercial term "platinum" generally refers to the whole group. These elements differ from iron, cobalt, and nickel in their greater nobility, and in their even greater tendencies to form complex ions, or coordination compounds. Although the similarities in the properties are very pronounced, there are, however, distinct changes in both the
1.
The
triads: ruthenium,
horizontal and vertical periodic relations, as
is
indicated in
the following table of their oxidation states. (Cf Par. 36.)
TABLE
Fe
2,
2,
OXIDATION STATES
3, (4), 3, 4, 4,
6
6,
Co
7,
2,
3,
4 6
Ni
(1), 2, (3),
4
4, (6)
Ru
Os
(
)
(2), 3,
6, (7),
8 8
Rh
Ir
(1), (2), 3, 4, (6)
Pd
Ft
(1), 2,
(1), (2), 3, 4,
(1), 2, (3), 4, (6)
Very unstable.
Among the more important of these relations which may be pointed out are the similarity of the + 6 compounds of iron, ruthenium, and osmium to those of chromium, molybdenum, and tungsten; the similarity of nickel, palladium,
:
433
434
REFERENCE

;
[Ch.
XX
and platinum to copper, silver, and gold the formation of volatile tetroxides by ruthenium and osmium; the remarkable absorption of hydrogen by nickel, palladium, and platinum, and the increasing tendency to form complex ammonia ions shown by the elements on the right.
deposits in
The important platinum ores are placer which the metal occurs as small grains or nuggets, the most extensive deposits being those in Russia, Colombia, and Transvaal. The nickel ores of Ontario con2.
Occurrence.
amounts of platinum as the mineral sperrylite, PtAs 2 Crude native platinum generally contains all of the platinum metals. The following percentage compositions show
tain small
.
the usual range: Pt, 60-80; Fe, 5-10; Pd, 1-2; Rh, 0.5-2; Ru, 0.5-2; Os, 1-10; Ir, 1-10. In addition, metal known as osmiridium is found, which contains largely osmium and indium with small amounts of the other metals. The per-
centages of the elements in igneous rocks are extremely low, the approximate values being: Pt, 10~9 Ir, 10~ 10 Os, 10~ 10 n Rh, 10-", and Ru, 10~ 3. Metallurgy. Platinum is extracted from sand and gravel by washing and gravity concentration processes
;
;
,
similar to those used with gold (cf. VII). For the separation of the crude metal into its constituents, it is usually first
digested with aqua regia. This dissolves the greater part of the metal, but leaves a residue of any osmiridium, which is fused with zinc in order to render it soluble in acid. The
separation of the various metals from the solution then becomes a matter of qualitative analysis (Par. 35). 4. Properties and Uses of the Metals. The most im-
portant atomic and physical constants are summarized in
Table
II.
Ruthenium and osmium are grey like iron, while the other metals are more like silver. Rhodium is one of the
whitest of
of
all
the metals.
is brittle,
Osmium
has the greatest density

glass.
any metal,
and hard enough to scratch
4]

are a
little softer,
435
and palladium and platinum very malleable. When the metals are formed by the decomposition of their compounds at comparatively low " temperatures, they are left in a finely divided or spongy"
condition.
Rhodium and indium
Hydrosols, or colloidal solutions, are readily prepared by striking an arc between electrodes of the metals under water.
TABLE
II
Spongy palladium and platinum, like nickel, show a remarkable catalytic effect upon many gas reactions. The
use of platinum as a catalyst in the manufacture of sulfuric acid, ammonia, and nitric acid, has been mentioned.
Platinum causes the instant explosion of a mixture of oxygen and hydrogen, or the ignition of alcohol vapor in air. An electrode coated with finely divided platinum, called platinum black, has a very low overvoltage for hydrogen
and other
gases,
and
is
often employed in the construction
436
REFERENCE
[Ch.
XX
where a reversible gas electrode is desired. surface may be prepared by the electrolytic precipitation of the metal from a chloroplatinate solution. Spongy platinum and palladium absorb large volumes of many gases, the absorption of hydrogen by the latter being especially remarkable (Par. 27).
of electrical cells
The platinum black
of the platinum metals in the more important industries is given in Table III. Commercial
The consumption
is
platinum
pecially iridium
usually alloyed with the harder metals, esand rhodium, to make it more durable.
The average
price per ounce in 1946 for the pure metals
was
$24; iridium, $125; and platinum, $35. fluctuations in the prices are quite large.
ruthenium, $35; rhodium, $125; osmium, $50; palladium, However/ the
TABLE
ill
S.,
CONSUMPTION OF PLATINUM METALS IN U.

Values in Troy Oz.
1948
5.
ity,
Platinum, due to its high melting point, incorrodibiland malleability, is almost indispensable in the manu-
facture of chemical utensils for high temperature ignitions. Such ware, however, must be handled with some care since
it is attacked by a number of reagents, e.g. aqua regia, chlorine solution, ferric chloride, and fused alkalies. It
many metals, especially lead, tin, bismuth, and mercury; and unites with carbon, phosphorus, sulfur, and However, alkali carbonates may silicon, becoming brittle. be ignited in platinum crucibles without damage. Alloys of palladium and gold such as "palau," are employed to some extent as substitutes for platinum in chemical ware.
alloys with
7]
437
pure platinum or platinum-iridium alloys are subjected to high temperature for a long period, appreciable loss of weight occurs, doubtless due to the formation of
When
Platinum-rhodium alloys, however, are much less subject to such 'Volatilization/' Platinum-iridium alloys are employed in the electrical industry in contact points. 6. Reactions of the Metals. The more important reactions are summarized in Table IV. Reference should be made to the paragraphs dealing with the states of each All of the element for approximate potential values.
oxide.
metals exhibit "passivity" with strong oxidizing agents, so that they are not dissolved by as many reagents as the potential values would indicate. (See also Par. 5 for additional reactions of platinum.)
TABLE
IV
REACTIONS OF PLATINUM METALS
RUTHENIUM COMPOUNDS
7.
Oxidation States.
large
number
of
Ruthenium assumes an unusually different oxidation states, 2, 3, 4. 6, 7, and
438
REFERENCE
[Ch.
XX
8. Compounds of the higher states in acid solutions are powerful oxidizing agents, and are reduced to salts of + 3 ruthenium. The metal is oxidized in alkaline solution to ru-
ruthenate, RuO 4 perruthenate, RuO4 ~, or the tetroxide RuO4 with the potential increasing for each
thenite,
RuOa
step.
The
following are approximate potentials for the
more
important couples:
VOLTS
*<>
+ 5C1- . RuClfi + T + H O - RuCUOH + H+ + e~ RuCUOH -f 3H O - RuO + SCI- + 7H+ + 4<r Ru + 6OH- - RuOr- 4- 3H O + 4e~ RuOr- -f 2OH- - RuO + H O + 2er
RU+-:
Ru - Ru++
-f 2e~
2
RiiCU
"
- 0.45 - 0.3 - 1.3 - 1.5
0.3
0.6
2 State. The fact that the oxide, RuO, does to exist indicates that in alkaline solution this not appear state is unstable, probably decomposing to give the metal
8.
The
and ruthenate (+6).

In acid solution, halides of Ru + + may be prepared by the reduction of the + 3 compounds by zinc, hydrogen sulfide, or by cathodic reduction. The solution has an azure blue
color; solid
in air.
cesium ruthenium chloride, Cs 3 RuCl5'2H 2 0, has been obtained from it, but the salt is rapidly oxidized
f
Potassium ruthenocyanide, K4 Ru(CN) 6 3H 2 O, is comparatively stable, and forms when ruthenium compounds of higher states are fused with potassium cyanide. It resembles ferrocyanide in the solubilities of its salts, and is
oxidized
9.
by chlorine, probably to the + 3 cyanide. The + 3 State. The chloride, RuCl 3 is formed when
,
the finely divided metal is oxidized by chlorine the complex is readily prepared by the reduction of 2 RuCl 5 chloride, the 4 complex, by alcohol, or other mild reducing
;
agents.
The
chloride in solution forms a bright red
ammonia
12]
439
complex, and with alkalies precipitates the hydrous oxide,^ Ru 2Oa, which is not soluble in excess of reagent. The chloride forms a complex with nitric oxide, RuCl 8 2 O, and a large number of alkali complex chlorides have been prepared, e.g. 2 RuNOCls, and 2 RuCl6H 2 O,
NOH
also the nitrite,
K Ru(NO
2
,
2) 5.
The bromide, RuBr 3 is actions. The iodide, RuI 3
similar to the chloride in its re,
is
but slightly soluble, and does

,
not appear to form complex alkali iodides. The dioxide, RuO 2 is obtained by 10. The + 4 State. the finely divided metal in air. It unites with metal heating
The sulfate, oxides to form ruthenites, e.g. BaRuOa. Ru(SO4 ) 2 may be prepared by oxidizing the sulfide, RuS 2 with nitric acid or by heating the tetroxide with sulfuric acid. The free tetrachloride has not been prepared; but the
,
potassium ruthenichlorides, K 2 RuCl 6 and K 2 RuCl 6OH, form when potassium ruthenate is dissolved in cold dilute
hydrochloric acid.
11.
2
The
4
K RuO 'H
and
7 States.
Potassium ruthenate,
is
2 O, forms when the metal
hydroxide and nitrate. It is orange red solution. With cold dilute hydrochloric acid, the complex ruthenichloride is formed, but the ruthenyl chloride, RuO 2 Cl 2 probably forms as an intermediate step. When acted on by chlorine at 60, the solution becomes dark green through the formation of perruthenate, RuCV". The alkali salts of the latter have been obtained as black crystals possessing a green metallic luster. 12. Ruthenium Tetroxide. The tetroxide forms in small
,
fused with potassium soluble in water, forming a deep
finely divided oxidation of an alkaline metal, but is best prepared by the solution of ruthenate, or by the action of hot nitric acid
quantities
by the action
of
oxygen upon
and perchloric acids on compounds of the lower oxidation states. The oxide melts at room temperature to an orange liquid, decomposes around 106, and unlike osmium tetroxIt is somewhat soluble in water, ide, it is not poisonous.
440
REFERENCE
[Ch.
XX
but the oxide seems to possess neither acidic nor basic

properties to
any marked degree.
In acid solution,
it is
powerful oxidizing agent.
OSMIUM COMPOUNDS
13.
Oxidation States.
8.
3
,
Osmium
resembles ruthenium in
forming compounds
6,
of the positive oxidation states, 2, 3, 4,
and
OsCle"
OsCl 6
In hydrochloric acid osmium may be present as or The oxidation-reduction po2 OsO 5

,
tentials
are extremely complicated, since almost every negative ion gives a different complex ion with the lower
states.
VOLTS
OsCl 6 3 + 3er ................................... OsClr 3 - OsCl 6 + e~ ...................................... 6C1- + 8H+ + 4*r ................. OsCle 4- 4H 2 O 4 = OsO 4 Os + 4OH- - OsO 2 + 2H 2 O + 4e~ ............................
Os
-f
6C1-
OsO 2
Os
+ 4OH- = OsO + 9OH- = HOsOfi4
+ + 2H O + 2e~ ........................ + 4H + Se~ .........................

2
2
,
-0.6
0.85
1.0
0.15
0.1
0.02
14. The + 2 State. The chloride, OsCl 2 has been prepared by heating the trichloride at 500, but neither it nor complex chlorides appear to have been prepared in solution. The slightly soluble iodide OsI 2 is precipitated when ~ iodide is added to OsCl 6 3 It is claimed that the reduction of the tetroxide with sulfur dioxide yields the sulfite,
.
OsSOa; and this, when heated, gives the oxide, OsO. The complex cyanides, e.g. K4Os(CN) 6 are probably the most stable compounds of this state. 16. The + 3 State. The chloride, OsCI 3 -3H 2 O, has been osmic acid with alcohol in the presprepared by reducing ence of chloride. When treated with sodium carbonate, the
,
sesquioxide,
Os 2 O 3
is
formed.
The
salts
2
K OsNOCl K Os(NO
5,
2
following are some of the more important complex of this state: 3 OsCl 6 (potassium chlorosmite),
2) 6,
KOs(NO)0 2
The
latter
com-
8]
PLATINUM
AND PALLADIUM METALS
441
pound, called potassium osmiamate, is obtained by the ammonia on a cold alkaline solution of the tetroxide. It dissolves in hydrochloric acid to form the complex*
action of
chloride.
16.
The
about 700
4 state. Chlorine reacts with the metal at to form the tetrachloride, OsCl 4 It slowly hy. -
drolyzes in water to the hydrous dioxide, OsO 2 Among the complex salts of this state are 2 OsCl 6 (potassium chlorosmate), and Na 6 OsCl 2 2 OsBr 6 2 OsI 6
(S0,) 4
17. The + 6 State. The trioxide is not known, but the metal fused with potassium hydroxide and nitrate gives potassium osmate, 2 OsO 4 and this salt is also prepared by reducing an alkaline solution of this tetroxide with alcohol. Barium osmate, BaOsO4 It is unstable in acid solution. is but slightly soluble. Some hexafluoride forms when fluorine is passed over the metal at 250. It is decomposed
by
water.
Many
OsO 2 Cl 4 OsO 3 Cl 2
solution.
18.
is
complex osmyl ions have been prepared, e.g. OsO 2 (C 2 O 4 ) 2 OsO 2 (NO 2 ) 4~, OsO 3 (NO 2 ) 2 None of the ions appear to be stable in acid
, ,
',
Osmium
Tetroxide.
The
formed by direct combustion
volatile tetroxide, of the metal in air, or
OsO4
by
its
oxidation with hot concentrated nitric or sulfuric acids.
The vapor has an odor resembling chlorine and is extremely poisonous. The oxide is soluble in water, but the solution 13 is only very slightly acid (Ki for H 2 OsO 5 is 8 X 10~ ). Alkalies form weakly bound compounds, e.g. OsO4 2KOH,
which are readily
line.
soluble,
and
their solution
is
is
highly alka-
As
indicated in Par. 13, the oxide
a powerful oxidiz,
ing agent.
The octafluoride, OsF8 and probably the chloride, OsQ 8 form in small amounts when the metal is heated in the These compounds are highly volatile and hyhalogen.
,
drolyze to the tetroxide in water.
442
REFERENCE
[Ch.
XX
RHODIUM COMPOUNDS
19.
Oxidation States.
Rhodium forms compounds hav-
ing as positive oxidation states 1, 2, 3, 4, and 6. Of these 4 are the more important. Unstable Rh 2 O 3 and the
and RhCl have been prepared. The

.
ion, Rh"*"* is
,
probably
readily oxidized to RhCl 6~3 Rhodic ion, Rh+++, resembles cobaltic ion in the nature of its coordination compounds, and the dioxide is
is
stable but in the presence of chloride
somewhat
Rh - Rh++
similar to cobalt dioxide.
+ 2eRh++ - Rh+++ + c~ Rh^ + 2H O - RhOj + 4H+ + e~ RhCl- -f 2H*O - RhO + 4H+ + 6Q- + e~
2 a
ca. < ca.
VOLTS
0.6
0.7
1.4
ca.
1.4
metal
+ 3 State. The oxide, Rh 2O 3 results when the heated in air below 1150. Above that temperature, the oxide decomposes into the metal and oxygen.
20.
The
is
The hydrous oxide is precipitated from rhodium solutions by alkalies, and is somewhat soluble in excess of concentrated alkali, doubtless with the formation of rhodites.
The
trichloride,
RhCl 8 may be prepared by heating the

,
metal in chlorine, and the salt so obtained is not soluble in water or acids. However, hydrated chloride formed by dissolving the sesquioxide in hydrochloric acid,
,
is
highly del,
iquescent. The bromide, RhBr 3 and iodide, RhI 3 have also been prepared. The latter is not readily soluble in hot water. The sulfate, Rh 2 (SO4 ) 3 forms alums. The sulfide, Rh 2S 3 is precipitated from acid solutions by hydrogen
,
sulfide;
but
compound
excess of hydrogen sulfide is employed, the Rh 2S 3 3H 2 S appears to form, and normal sulfide
if
precipitates but slowly.
The following coordination compounds are analogous to the corresponding cobalt compounds: 3 [RhCl 6 ], Na 2 [RhC1 6 20], [Rh(NH 8 ) 6 ]Cl 3 [Rh(NH 8 )*Cl]Cl 2 K,[Rh(CN)J.
and K,[Rh(NO,)J.
23]
PLATINUM
443
*
21. Rhodium Dioxide. Powerful oxidizing agents in alkaline solution, e.g. CIO"", convert the sesquioxide into the dioxide, RhO 2 The dioxide is not soluble in water or
.
but dissolves in hydrochloric acid with the evolution of chlorine. Continued action of sodium hypochlorite on the dioxide gives a blue solution which is thought to
alkalies,
contain sodium rhodate,
Na RhO4
2
IRIDIUM COMPOUNDS
22.
Oxidation States.
The important
oxidation states
3 and 4. Powerof iridium, like those of rhodium, are ful oxidizing agents in alkaline solutions form iridates
(+6), but these are not
stable in acid.
The
solid chlorides, IrCl
compose
chloride.
in the presence of
and IrCl 2 are stable but dewater to the metal and the + 3
,
VOLTS
Ir
26
11-+++
2H 2 .Ir++ + Ir0 2 Ir IrCl 4 3 6C1-
IrClT 1 - IrCl 6 + er Ir0 2 + 40H- - Ir0 4
+ 3e~
-2
+ 4H+ + + 3er
2
<r
+ 2H O + 2e~
The
,
- 1.0 ca. - 0.7 - 0.72 - 1.02 > - 0.4

ca.
23.
The
3 State.
the finely divided metal is not soluble in water, but the hydrated salt formed by dissolving the sesquioxide in hydrochloric acid is readily soluble. The chloride forms complex salts with the alkali chlosimilar compounds are formed by the 3 IrCl 6 rides, e.g.
trichloride, IrCl 3 forms when is heated in chlorine. This product
bromide and iodide*
These compounds are most readily

,
prepared by reduction of the + 4 complex salts in acid solution. With alkalies, the sesquioxide, Ir 2 O 3 is precipitated, and is soluble in excess of the reagent. With hydrogen sulIridium fide in acid solution, the sulfide, Ir 2 S 3 forms.
,
sulfate, Ir 2 (S0 4 ) 3
forms alums.
salts are the cyanide, e.g.
Other important complex NaJr(CN) 6 and nitrites, e.g.

,
Ir(N0 2 ) 6
444
REFERENCE

,
[Ch.
XX
4 State. The dioxide, IrO 2 is obtained when 24. The the finely divided metal is heated to 1100 in air. hyform results from the oxidation of the sesquioxide in drated air, from the addition of alkalies to the chloroiridates, and
upon solution
in
water of alkali
iridates.
It is soluble in
hydrochloric acid and in sulfuric acid, yielding the chloride and sulfate in solution. The solid chloride is a dark brown
substance very soluble in water and forms stable complex

chlorides, e.g.
26.
IrCl 6
Hundreds
of
complex ammines and

,
Potassium iridate, K 2 IrO 4 appears to be formed when the metal is fused with potassium hydroxide and nitrate, but oxygen is evolved when the salt is dissolved in water and the dioxide precipitated.
halogen compounds
are known.
The
6 state.
PALLADIUM COMPOUNDS
principal states of palladium, platinum, are + 2 and + 4. There is some evidence for the formation of the monochloride upon heating the dichloride, but in general the + 2 compounds decompose
like
26. Oxidation States.
The
directly into the metal at high temperatures.
The
trioxide
PdOa has been

Pd - Pd++
PdCl 4
reported.
VOLTS M
Pd Pd
+ 4C1- = PdCl + 2e~ + 20H- - Pd(OH) + 2er

4
2
+ 2C1- -
2e-
PdCl 6
~ + 2e~
0.83 0.29
0.64
0.1
Palladium absorbs hy27. Palladium and Hydrogen. drogen to a remarkable extent, 600 to 900 times its own volume at 25, depending somewhat upon the physical condition of the metal.
pressure-concentration curves for the system indicate the formation of a solid solution of the metal and the hydride of empirical formula, Pd 2 the ab-
The
sorption accompanied by a considerable increase in the volume of the metal. The gas is almost completely evolved, in vacua at 100. The hydrogenated metal is a good reducing
is
29]
PLATINUM
445
agent, e.g. reduces mercuric chloride and ferric salts, and also induces the oxidation by oxygen of many carbon com-
pounds, possibly through the formation of hydrogen peroxide:
Pd 4 H 2
2.
+O =
2
4Pd
+HO
2
and
H O + CO
2 2
HO
2
+ C0
2 State. The halides are formed by heating 28. The the metal in the halogen. The chloride, PdCl 2 -2H 2 O, is
soluble in water,
and with alkalies gives a precipitate of the hydrous oxide, PdO. This is soluble in concentrated ammonia, forming a complex ammonia ion, and upon dilution and acidifying slightly with hydrochloric acid, a precipitate of the diammoniate, PdCl 2 '2NH 3 is obtained. The iodide, PdI 2 and cyanide, Pd(CN) 2 are but slightly soluble in
, ,
,
water, but dissolve in excess of the precipitating ions. The sulfide, PdS, is precipitated from acid solutions by hydro-
gen
sulfide.
It is
not soluble in
ammonium
sulfide.
The
sulfate
The
2 2
K [PdCl Ag2 [PdCl -(OH) K K [PdBr (NO [PdCl -2CO].

4 ], 2
and nitrate are readily soluble. following types of complex salts have been prepared :
2 ],
[Pd(CN) 4 ],
Na 2 [Pd(NO
2)4]
2 ) 2 ],
These tetra-coordinated complex ions are planar and not

tetrahedral.
The planar character of
Pd"
""
1
is
also illustrated
by the crystal structure of the chloride PdCl 2 in which infinite polymerization occurs to give strings of planar groups.
VVVVV
Cl
Cl
'
29.
4 State. The hydrous dioxide, PdO 2 -nH 2 O is obtained by anodic oxidation of an acid solution of palladous nitrate. A precipitate of the sesquioxide, Pd 2 O 3 probably PdO-PdO 2 first forms but is decomposed by the acid leaving the dioxide. The dioxide decomposes around 200 to the monoxide. The tetrachloride and bromide have not been prepared in
The
446
REFERENCE
[Ch.
XX
the pure state, but alkali complexes of the type

are known.
PdCl 6
,
prepared by or by dissolving the dioxide in potassium chloride and hydrochloric acid. It is only slightly soluble in cold water and the same is true of the ammonium salt.
rine,
is 2 PdCl 6 chloropalladate, the oxidation of the chloropalladite by chlo-
The potassium
PLATINUM COMPOUNDS
30. Oxidation States.
series of
Platinum forms two important
to the oxidation states and, in addition, a few comparatively unIt stable compounds of the 1, + 3, and + 6 states. exhibits strong tendencies to form coordination complexes and the simple salts are, in general, either insoluble or
compounds corresponding
and
+ 4,
slightly ionized in solution. For this reason, the oxidationreduction potentials for the various oxidation changes
depend very much upon the negative ion present.

2e 4C1- - PtCl 4 2H+ Pt 2er 2C1- - PtCV PtCl 4 2er Pt - Pt++ 2e~ 4Br~ - PtBr 4 Pt 2<r Pt 2OH- - Pt(OH) 2
~+
+
VOLTS
ca.
25
+ +
'.
ca.
Pt(OH)s Pt(OH) 6
+ ~ 4OH- - Pt(OH) + 2OH- - PtO

4
+ 2er
ca.
4-
4H 2 O
+ 2tr
,
0.73 0.72
1.2
0.68
0.16
0.2
0.4
2 State. Platinous chloride, PtCl 2 is gen31. The erally prepared by heating the tetrachloride or chloroplatinic acid. It also forms when spongy platinum is heated
in chlorine at
not soluble in water, but dissolves in excess of hydrochloric acid to form a solution of chloroThis acid is most conveniently platinous acid, H 2 PtCl 4
It is
.
200.
prepared, however,
by
sulfur dioxide.
by The
the reduction of chloroplatinic acid

alkali
and ammonium
salts,
e.g.
potassium chloroplatinite, KgPtCL. ^re soluble; but the

silver
and lead
salts are not.
33]
447
The chloride forms many addition compounds, for example, PtCl 2 CO and PtCl 2 -PCl 3 The fluoride is soluble, but the bromide and iodide are not. The latter decompose readily: 2PtI 2 = Pt + PtI 4 Platinous hydroxide, Pt(OH) 2 is prepared by boiling chloroplatinites with equivalent quantities of alkali. With excess of alkali, it decomposes, forming the metal and
.
. ,
platinates.
It is soluble in the
halogen acids, but not
in
oxy-acids.
The black
fide is
sulfide, PtS, precipitates when hydrogen sulpassed into a solution of chloroplatinite. It appears
to be even less soluble than HgS. The more important coordination
compounds
of
2
,
platinum are given below. The nitroplatinate, Pt(NO 2 ) 4 is especially stable, as the platinum is not precipitated by alkalies or hydrogen sulfide, and strong acids form the
nitro-acid,
Like Ni"*" 4 and Pd ++ these compounds have planar coordination instead of tetrahedral.
2
Pt(NO 2 )4.
"
Platino-coordination Compounds.
M M M
2
2 2
[PtCl 4 ]
[PtBr4
M M
2) 4]
2 2
[Pt(CN) 4 [Pt(CNS) 4
]
[PtCl 2 (NH 3 ) 2 ]
]
[Pt(NO
M[PtCl 3 -NH 3
[Pt(NH 3 ) 4 ]Cl 2 M[Pt(CNS) 3 CO]
32.
The
high temperatures.
following
.
The trichloride may be formed at When warmed with hydrochloric acid the decomposition occurs 2 PtCls + 4C1~ = PtCl
3 State.
:
There is + PtCle ~ Pt 2 Os. The complex cyanide ion Pt(CN) 4 is stable. 33. The + 4 State. When platinum is dissolved in aqua regia, chloroplatinic acid is formed in solution; and upon removal of nitric acid by excess of hydrochloric acid, the hexahydrate, H 2 PtCl 6 -6H 2 O, may be obtained by crystallization.
some evidence for the sesquioxide
The aqua
regia solution
also contains the

.
nitrosyl chloroplatinic chloride, PtCl 4 (NO) 2 Cl 2 By igniting the chloro-acid in an atmosphere of chlorine, the tetrachloride PtCl 4 is obtained. This salt is soluble in water, and
,
448
REFERENCE
[Ch.
XX
C1 2 The to 370 decomposes :PtCl 4 = PtCl 2 trichloride probably forms as an intermediate step. The chloroplatinates are the most important compounds of the metal. The silver and cesium salts are insoluble, and
when heated
the rubidium, potassium, and ammonium only slightly soluble; hence these compounds are precipitated when the chloro-acid is treated with a solution of the corresponding
positive ion.
Platinum tetrabromide and iodide are analogous to the

chloride.
When the tetrachloride is heated with an excess of sodium is formed in hydroxide, sodium platinate, Na Pt(OH)
2
6,
solution;
upon neutralizing
this solution
with acetic acid

,
is prethe hydrated dioxide, PtO 2 2 O or 2 Pt(OH) 6 The oxide is soluble in the halogen acids, and in cipitated.
4H
sulfuric acid gives a solution of the sulfate,
Pt(SO 4 ) 2
Platinic sulfide,
PtS 2
is
of the chloroplatinate by in nitric acid, but soluble in
precipitated from acid solutions hydrogen sulfide. It is insoluble
ammonium
polysulfide.
Hundreds of complex platiniammino-salts are known in which platinum generally has the coordination number six. Examples of these complex types are: [Pt(NH 3 ) 6 ]X 4 [Pt(NH 3 ) 4 X 2 ]X 2 and [Pt(NH 3 )X 5 ]R. Nitroplatinites are oxidized by halogens with the forma, ,
tion of tetranitro dihalidoplatinates, e.g.
Complex
platinithiocyanides, e.g.
Pt(NO 2 )4Cl 2
,
Pt(CNS) 6
.
have been
prepared; but the platinocyanides are oxidized to the + 3 and not the 4 state, e.g. AgPt(CN) 4 34. Perplatinate. In alkaline solution, the platinates are coverted by anodic oxidation into perplatinate, e.g.
K PtO
2
4.
leaving an insoluble trioxide, evolves oxygen upon heating.

acid,
These compounds are decomposed by sulfuric PtO 3 which readily

,
general principles of the scheme for the separation of the platinum metals, given by Gilchrist and Wichers, are as follows
35. Analytical.
:
The
36]

is
449
distilling with absorbed in a solution of sulfur dioxide and hydrochloric acid. Ruthenium is next removed as the tetroxide by distillation after the addition of sulfuric acid and sodium bromate. The same absorbing agent is
Osmium
removed as the tetroxide by

is
nitric acid.
The gas
employed.
Rhodium, iridium, and palladium are precipitated and separated from platinum as the hydrous dioxides. The precipitation is made with sodium bicarbonate at about pH 6 from a chloride solution in the presence of sodium bromate. Platinum is precipitated from the filtrate after the addition of hydrochloric acid by saturating with hydrogen
sulfide.
dioxides of rhodium, iridium, and palladium are dissolved in hydrochloric acid and the palladium precipitated
The
with dimethylglyoxime. The latter reagent is destroyed in the filtrate by evaporation with sulfuric acid and the rhodium precipitated as the metal by titanous chloride. The titanium which has been added may be removed with
cupferron (C 6 6 N'N(>ONH4) and the iridium precipitated as the hydrous dioxide. After the isolation of the various elements, they are generally converted to the metal and weighed as such.
necessary to separate gold from the metal. This is readily accomplished by the preplatinum cipitation of the metal from a 1.2N HC1 solution by reducIt is frequently
tion with hydroquinone. The platinum metals remain in solution. In order to compare stability 36. Potential Diagrams.
triods,
relationships in the various oxidation states of the three the following potential diagrams are given for
It will be noted that for any family (i.e. acid solution. same number of electrons), the elements become more noble or more electronegative with increasing atomic weight, but the higher oxidation states become relatively more stable. This is particularly true of iron, ruthenium and osmium.
450
REFERENCE

-f4
[Ch.
XX
Fe
Ru
Os
I
- - - - - - 0.44
+2
+3
-0.77 Fe++
- 0.45
- 0.3
Ru**
QS++
RuCU"2
- 0.7
0.3
OsClr8
|
-0.6
-+6
+7
<-1.9
1.3
+8
1.7
1.6
RuCUOH-
HRuOr
OsCl 6
~2
RuO 4"
1.0
-1.0
RuO<
0.85
OsO 4
0.277
1.82
(-0.6)
i
(-0.9)
(-1.4)
(-1.4)
Rh++ (- 0.7)
Rh+++
|
RhOa
HRhO "
4
<-1.0
>-1.0
(-1.2)
0.25
Ni++
1.75
< NiOs
1.8
Ni
HNiOr
pd
I
1
0.98
< Pd -hf
PdCl 4
1.6
Pd +4
~~
1.29
0.64
PdCle""
(-1.1)
.
(-1.2)
Pt
I '
^
PtO2
Pt^
0.73
Ptci 4
0.72
ptcir~
Chapter
XXI
SCANDIUM, YTTRIUM, AND THE RARE EARTH ELEMENTS

Following barium, atomic number 56, there occurs a group of 15 remarkably similar elements known as the Rare
1.
Earths, which form
3 ions resembling those of scan-
dium and yttrium, the two preceding elements of Main Group III. The existence of this group was long a puzzling
problem, as the older forms of the periodic table predicted but one element at this point. The explanation is now given in terms of the electronic structure of the atoms. The distribution of electrons in the various quantum levels in lanthanum, 57, and lutecium, 71, appears to be as
follows
:
to lanthanum, no electrons have gone into the 4/ level, 5s, 5p, and 6s quantum levels represent lower energies since, in terms of the Bohr picture, electrons in these highly elliptical orbits are on the average closer to the nucleus. When these levels are occupied, the 4/ levels then become the next most stable positions, and as 14 electrons
Up
as the
are required to fill it, we find this group of 15 elements with the same number of outer or valence electrons, and differing only in the number of electrons in a level comparatively
451
452
REFERENCE

The elements
and thus
give
all
[Ch.
XXI
deep within the kernel.
and 6s electrons La+++
fairly easily,
up their Sd form ions like
The history of the rare earths dates from the discovery (about 1800) of two earth-like oxides which were given the names yttria and ceria. Further study of these oxides has resulted in the discovery of all the rare earth elements, except element 61 (cf. Pan 11). Although crude ceria and yttria generally contain at least traces of almost all of the other rare earths, the former consists largely of the oxides of the elements of atomic numbers 57 to 62; and the latter of oxides of yttrium and the
elements 63 to 71; these groups are generally designated as the Cerium Subgroup and the Yttrium Subgroup. 2. The rare earth elements are so similar that it is ex-
two succeeding however, a gradual change in the properties in going from lanthanum to lutecium; for example, there is a slight decrease in the atomic volume and a corresponding slight decrease in the basic nature of the sesYttrium, being smaller than lanthanum, requioxide. sembles the heavier members more than it does the lighter ones. Scandium is less basic than yttrium, and resembles aluminum more than the other elements do. ++ with no electrons, is 3. Since La+ especially stable, / cerium tends to assume the same electron structure which it can do by forming a + 4 ion. Likewise, ytterbium tends to form the Lu" 4 4 structure (completed /shell) and in addition to Yb+ ++ forms Yb++. Gadolinium has one / electron in each of the seven / orbitals and Gd+ ++ is more stable than the + 3 ions of neighboring elements. Hence there is considerable tendency for europium to form Eu ++ and terbium to form Tb+4 It is interesting to note that the densities of
tremely
difficult,
in general, to separate
elements. There
is,
"
"
"
europium and ytterbium (Table I) are out of line with the other rare earth metals and resemble more nearly those of
the alkaline earth elements.
THE RARE EARTH ELEMENTS

4.
453
most of the rare earths are highly In completed electron shells, the orientation of the electron orbits appears to be such as to give zero resultant electrical moments, but this is not the case in
Compounds
of
magnetic (Table
I).
uncompleted groups. Thus lanthanum ion, La+++, and lutecium ion, Lu +++ are not magnetic; but the transitional elements between are highly so.
,
TABLE
PROPERTIES OF SCANDIUM, YTTRIUM, AND THE RARE EARTH
ELEMENTS
similar considerations apply to the colors of the rare earth compounds. Ions such as Na+, Cl~, La"*"*"*", and Lu"*"*" 4", which contain completed electron groups are 4 colorless; while ions of such as 0+++, Co "*, and most of
6.
Somewhat
the rare earths, which belong to transition groups, are generally colored. Characteristic absorption lines of the various
elements in solutions of their compounds offer an easy method for their detection. The atomic emission spectra are
readily excited in the electric arc.
454
6.
REFERENCE

It is
[Ch.
XXI
Occurrence.
estimated that
all
the rare earths
4 together constitute only 1.5 X 10~" per cent of the igneous rocks. The order of decreasing abundance of the members
given as: Ce, Nd, La, Y, Sm, Gd, Pr, Er, Yb, Lu, Dy, Ho, Tin, Tb, Eu, and Pm. It may be observed from this order that the elements of odd atomic numbers are, in general, much less abundant than the even-numis
of the group
bered elements; and that the Yttrium Subgroup is less abundant than the Cerium Subgroup. The approximate 7 percentage of scandium in the igneous rocks is 10~
.
The most important
source of the Cerium Subgroup
is
the mineral monazite, which is essentially RPO 4 (where R stands for any rare earth element). A typical composition
15.6; CeO 2 28.8; Pr6 O n 3.6; Nd 2 O 3 terbium earth oxides, 0.8; yttrium earth 11.4; 6.5; U 3 O 8 0.2; P 2 O 5 28.0; A1 2 O 3 oxides, 0.32; ThO 2 Brazil and Travancore in India are the SiO 2 2.5. principal producers of the mineral, which is generally found in alluvial deposits or sands, where it has concentrated due to the high specific gravity of the particles. A phosphate, xenotime, which contains largely yttrium
in per cent is:
La 2 O 3
Sm
O3, 1.2;
earths, also occurs.
an yttrium silicate of the approximate and cerite is the cerium group formula, Be 2 FeY 2 Si 2 Oi Yttrocerite is a rare earth silicate, H 3 [Ca, Fe]Ce 3 Si 3 Oio. with calcium fluoride, approximately RF</CaF 2 which contains about equal quantities of the two subgroups. Columbates and tantalates, such as fergusonite, (R) 2 O 3 [Cb,
Gadolinite
is
,
,
TaÔs, are found, often associated with thoria, and uranates. Mineral carbonates also occur.
zirconia,
PREPARATION AND PROPERTIES OF THE METALS

to the highly electropositive nature of the rare earths, the metals are difficult to prepare. The most satisfactory method is the electrolytic reduction of the oxide in
7.
Due
8]
THE RARE EARTH ELEMENTS]
455
the molten cloride.
Reduction with sodium or magnesium generally gives an alloy. An alloy of the metals of the cerium group is obtained from the rare earth residues of monazite sand, and is called Misch metal, or commercially "cerium." Its approximate
composition in per cent
rare earths, 10.
is:
Ce, 50; La, 25; Nd, 15; other

i.e.
It is highly pyrophoric,
if
scratched, especially
alloyed with iron, and
gives sparks if is used exten-
War,
sively for cigar lighters, gas lighters, etc. During the World it was used in tracer bullets and luminescent shells.
The metals of the cerium group, except promethium, have been prepared in fairly pure form; but those of the yttrium group have not, as the higher melting points of these metals and the greater volatility of their chlorides
render the electrolytic process difficult of operation. The melting points and densities are given in Table I. The lower melting metals are about as soft as tin, but the The cerium metals higher melting ones resemble iron. tarnish readily in moist air and ignite when heated. Cerium has a kindling temperature of 165, neodymium 270, and
lanthanum 445.
marized in Table
The most important

II.
reactions are sum-
TABLE
II
REACTIONS OF RARE EARTH METALS
4M 2M 2M 2M
+ 3O - 2M O + 6H O - 2M(OH) + 3H + 3X - 2MX* + Na = 2MN M + 2C - MC 2M + 3S - M S 2M + 3H 2MH

2
2
8
Slow
in cold
X denotes halogen
Forms with oxide when At high temperature
M burns in air
- M<0 +++
Reaction at comparatively low temperature
+ 3e~
La
+ 2.37
COMPOUNDS
Important solubility relations of the cerium and yttrium groups are summarized in Table III.
8.
(a)
The
3 State.
456
REFERENCE
[Ch.
XXI
is distinctly basic, and the hydroxides of the yttrium group, while less basic, do not dissolve in excess hydroxide. The sulfides, cyanides, simple sulfates, and halides, except fluorides, are all soluble.
Lanthanum hydroxide
of the yttrium but resembles the cerium family in the slight solubilgroup, Like aluminum, it ity of the double potassium sulfate. forms a complex fluoride ion, ScF4 ~.
Scandium forms a weaker base than any
TABLE
III
PROPERTIES OF RARE EARTH COMPOUNDS
+ 4 State. Cerium forms a well defined 4 compounds. In this state cerium is very + similar to thorium, and the element is often considered as a member of the fourth periodic group. Cerium dioxide is formed upon igniting cerous oxide. The hydrous oxide may be formed by the oxidation of cerous hydroxide in alkaline solution, or by the action of
9.
(6)
The
series of
11]
457
alkalies
upon
eerie salts.
It is soluble in nitric, sulfuric,
and
cold hydrochloric acids, giving the corresponding salts in The chloride solution readily evolves chlorine solution.
upon
It
heating.
The fluoride, CeF4

salts
O,
is
insoluble in water.
with the alkali fluorides. The iodate, is slightly soluble, resembling the thorium comCe(IO3)4, pound. Ceric ion is a powerful oxidizing agent. An accurate E value cannot be given as the activities are not known. In IM H 2 SO 4 and equal concentration of Ce ++4 and Ce+4 1.44 and in nitric and perchloric acids, the potential is 1.6. Ceric sulfate is a valuable volumetric rearound
forms complex
"
agent.
In most respects it is very similar to permanganate but is not as highly colored so that the end-point must be determined by using either a spot plate reagent or an oxidiz-
able dye.
Praseodymium, neodymium, and terbium all form diR 2 O 3 ) but they are even more powerful oxidizing agents than CeC>2 and difficult to
oxides (or solid solutions of RC>2 in
prepare pure.
10.
The
2 State.
Compounds
of
EU++, Yb++, and

1
Sin"
= Eu" 4 are known, the potential of the couple, Eu" e~ is 0.43 and the values for the corresponding couples for ytterbium and samarium appear to be about 0.6 and
1
"1"
""
1
"" "
1
0.8 respectively.
Thus Eu ++
liberate
is
the only one of the ions

"
"
1
hydrogen from water. It is " the reduction of Eu" 4 with zinc. The readily prepared by
1
which does not rapidly
+ 2 ions resemble
11.
Ba 4"* in the solubilities of their salts. 162 is a Radioactivity. The samarium isotope Sm
a-emitter
(half-life
naturally occurring
10 12 years)
and
Nd
150
and Lu
176
are
half-lives of 5
naturally occurring /3-emitters with 10 10 years and 2.4 X 10 10 years respec-
tively. The radioactivity of samarium and neodymium are of interest with respect to the stability of element 61. The
claims for the existence of this element (formerly called illinium) in nature have not been substantiated. The first positive identification of an isotope of element 61 was made
4-
I! a co
? O s
.3
23
I
'a
8 Z
T)
%
5
P
Pi-aci > U _- B
P
3
1 s
ts
s^yly ||!| M
trt
ffl
fl
SB
a>
**
18
I
8
5Q
oju
S^:
a*o
s*
2 ^ 1-55
d
fi|
s|QS S llÎ
TJ
-<
I*
s
ctf
CQ
"
43
"S
S
.5
IglgQ
3 -
i
!
37
'a
OJ
^
Z^
IH "HJ
8
M
..
rt
^.S
.^S
!I!l
!S
Solu
458
12]

fission
459
147 products of uranium. The isotope 61 with a half -life of 3.7 years is produced with a fission yield of 2.6 per cent. The operation of a uranium pile at a power of 10 5 kw. will produce about 1.5 grams of the isotope per The name promethium from the Greek god day. " Prometheus/' the giver of fire, has now been given to element 61.
from the
Separation and Analyses. A fairly satisfactory method of separating scandium, thorium, and most of the members of the cerium subgroup is outlined in Table IV.
12.
H H H H
FIG.
1.
Schematic
resin.
representation of cation exchange Picture courtesy Dow Chemical Company.
separation of the neighboring elements of the yttrium rare earth group was formerly accomplished only by repeated fractional crystallization or precipitation. Thus, in the original separation of ytterbi&m and lute-
The complete
cium, 15,000 crystallizations were made. The separation of neighboring members of the rare earths is now readily
460
effected
REFERENCE
[Ch.
XXI
of the ion-exchange resins (cf. Fig. 1). consists essentially of absorbing the mixed process rare earths on the top of a long column packed with
by mean
The
Amberlite resin. The column is then eluted by pouring through one per cent citric acid solution (in the pH range Under these conditions both the front and rear 5.0-5.5).
150
120 Cm
MOO
SO
40
45
Volume
50
of Eluate, Liters
55
60
FlG.
2.
Nd 2O 0;
Elution curves for sample containing equal weights of SrrÔs Pr 6Ou 3. Picture courtesy Dr. F. H. Spedding. 3
O;
edges of the elution bond (amount of rare earth eluted per liter plotted against liters of the eluant passed through
the column) are steep and the front edge of the one rare earth bond is riding on the rear edge of the proceeding
in Fig. 2. The ion-exchange resins have been equally successful in separations of the actinide
bond as indicated
elements.
The yttrium group is commonly divided into three subgroups, and the members of each subgroup are usually
separated as indicated below:
121
461
Chapter XXII
THE ACTINIDE ELEMENTS

1.
The chemical
properties of thorium and protactinium
resemble those of hafnium and tantalum respectively, but the properties of urariium and tungsten are markedly different. Thus tungsten is seminoble metal and uranium
6 state of tungsten is The highly electropositive. 6 uranium is a fair oxidizing agent and inert and quite the oxide is readily soluble in acids and bases. The lower oxidation states of tungsten are stable only in the form of complex ions which tend to complete the 5d, 6s, 6p shells 4 states of uranium The 3 and such as W(CN)s~ 4 exist in aqueous solution as the simple ions; they do not
is
form highly stable complex ions with cyanide and
in general
their chemical properties are similar to those of the rare earth elements. With the discovery of the transuranium elements neptunium, plutonium, americium, curium, berkelium and californium it became obvious that these elements contained electrons in the 5/ shell. The point at which the energy of the,5/* shell drops below that of the 6d is somewhat uncertain and may depend upon the physical state of the element and its chemical environment. An of the spectroscopic data for the gaseous interpretation atoms leads to the following electron assignments for the valence electrons, but the distribution in the various shells
462
2]
463
is
all
doubtless different for the elements as metals. The overevidence justifies the assumption that the 5/ series starts
with thorium and these elements

"actinides" in the
may
be called the
same sense that the
rare earths are called
"lanthanides."
2, The binding energies of the 5/ electrons are less than those for the corresponding 4/ electrons and, as a consequence, the number of electrons which may be removed by
oxidation
is
greater.
plutonium However, as the number of 5/ electrons increases the stability of the higher oxidation states decreases and the stability of the + 3 state increases, that is, the elements become increasingly "rare earth" in character. This is evident in the potential values given in Table I.
all
Thus uranium, neptunium and have well defined + 6 oxidation states.
TABLE
OXIDATION POTENTIALS IN AQUEOUS SOLUTION VALUES IN VOLTS FOR EQUAL ION CONCENTRATION
comparison of the various oxidation states for the is given in Table II, the values in brackets are for states which exist only as solids, i.e., they are unstable in water solutions.
actinide*'and lanthanide elements
TABLE
II
OXIDATION STATES OF LANTHANIDE AND ACTINIDE ELEMENTS
464
REFERENCE

TABLE
II
[Ch.
XXII
(Cont'd)
3.
series are colored in those oxidation states in
Like the rare earths, the elements of this actinide which one or
more / electrons are present. In general the absorption bands are sharp as a consequence of the shielding of the / electrons by the other electron shells. The absorption spectra in aqueous solution may be employed for the quantitative and semi-quantitative determination of the elements. As the number of electrons in the / shell increases, there is a contraction of the ionic radii as noted for the rare earth elements. As shown in Table III the ionic
than the values for the corresponding rare earth. Because of the similarity of the ionic radii, neighboring elements have compounds with isoradii are only slightly larger
TABLE
III
IONIC RADII OF ACTINIDE AND LANTHANIDE ELEMENTS
morphous structures and

are:
identical crystal types.

,
Examples
,
ThF 4 UF 4 NpF AmCl 3

, ,
4,
PuF 4 and UC1 3 NpCl 3 PuCl 3
Theoretically, similar lanthanide and actinide ions might be expected to have the same magnetic moments
4.
6]
465
4). A comparison is given in Fig. 1. The lower (cf. XXI values for the actinide elements appear to be due to the
6000
Nd
(HI)
Pr
(III)
5000
Eu
(III)
14000
'3000
Ce
(III)
.2000
1000
01
FIG.
1.
234567
Am
(III)
Number
of f Electrons
Plot of molar magnetic susceptibilities of some aqueous actinide and lanthanide ions.
breakdown
elements.
of
the
spin
vectororbital
vector
of the
(Russell-
Saunders) coupling which
occurs in
all
heavier
ACTINIUM
5.
Occurrence.
,
The most
stable actinium isotope
is
the
Ac
half-life 21.7 years. Although it has long been recognized that this isotope always occurs in uranium ores, the 235 has only recently origin of the actinium series in
227
been
6.
established.
The chain
is
U -VTh
235
231
separated from uranium ores along with its isolation from these elements is the rare earths, difficult, especially since its beta radiation is difficult to
Actinium
is
and
466
detect,
REFERENCE
[Ch.
XXII
and
sufficient
its presence cannot easily be determined until time has elapsed to build up its decomposition
products. The best source of the isotope Ra 226 radiated with pile neutrons: Ra 226 (n,7)
Ac 227 is from Ra 227-^>Ac 227

.
TABLE
IV
ACTINIUM ISOTOPES ATOMIC NUMBER 89
The
short
life
of
mesothorium
II
Ac 228
leads to its presence
only in extremely Like the rare earths, the potassium 7. Chemistry. complex sulfate, the fluoride, and oxalate are slightly soluble, though the latter dissolves readily in dilute acids. It is not precipitated by hydrogen sulfide. The hydroxide
is
small quantities in thorium.
more basic than lanthanum, is only partially precipitated by ammonium hydroxide, and dissolves readily in am-
monium
salts.
THORIUM
8.
Occurrence.
It is
10~~
6
Table V).
12
isotope is Th (cf estimated that the igneous rocks contain
The most important
232
of thorium per gram of rock. Monazite, the rare earth phosphate mineral, generally contains 2 to 10 The deposits of beach sand in per cent thoria, ThC>2. Travancore are the principal source of the element. Brazil
grams
9]
467
ranks second in the production of monazite and there is a small domestic production from the sands and gravels of North Carolina, South Carolina and Florida. Other ores are thorianite, a mixed oxide of ThO 2 and U 3O g and
,
thorite,
extracted from its ores by digestion with hydrochloric or sulfuric acids. Ammonia and the alkalies precipitate the hydroxide, which is not soluble in excess of the reagent. Thorium and cerium are separated from the rare earths through the very slight solubilities of the iodates, Th(IO 3 )4 and Ce(IO 3 )4, even in rather concentrated acid. Thorium may be separated from cerium by
ThSiO 4 Thorium is readily

.
reduction of the latter to the
3 state.
TABLE V
THORIUM ISOTOPES. ATOMIC NUMBER 90
9. Thorium Metal. Because of the highly electropositive character of the element, the metal is extremely difficult to prepare.
Th = Th+4
+ 4e-
E =
ca 2.06
However, the reduction may be carried out by heating the dioxide with calcium in a bomb. The melting point is
468
REFERENCE
[Ch.
XXII
1845 C. the boiling point is around 4200 C. and the density 11.2. It may also be prepared by the electrolysis The electrical of the fused complex fluorides, 2 ThF 6 10~ 6 ohm-cm. The metal is is given as 10 resistivity soft and malleable. There are no important uses at present,
but the possibility exists of using thorium as an atomic 233 fuel for the production of U 16). (cf. XXIII Thorium dioxide, or thoria, appears to 10. Chemistry. possess no acid properties, even when fused with alkali, and The in this respect differs from zirconium and hafnium. oxide dissolves but slowly in acids, but the unhydrated hydrated form, ThO 2 -2H 2 O, or thorium hydroxide,
The hydroxide is is readily soluble in acids. formed as a gelatinous precipitate upon the addition of alkali hydroxides or ammonia to thorium salts in solution. Lower oxides have not been prepared, but a hydrated peroxide is formed by the action of hydrogen peroxide upon solutions of thorium salts; the formula appears to be
Th(OH) 4
Th 2 O
4H
O.
Mixtures of thorium and cerium dioxides, heated to high temperature, exhibit a brilliant white luminescence, the maximum emissibility being obtained with about one percent of cerium dioxide. Advantage is taken of this fact in the Welsbach gas mantles, which are manufactured by saturating fabric with the nitrates of these metals. When
ignited, the oxide residue retains the shape of the original few per cent of beryllium and magnesium nitrates fabric.
are usually added to give the ash greater strength. The dioxide is employed in the manufacture of laboratory
crucibles to stand temperatures as high as 2300 C. The tetrahalides are prepared by methods characteristic
of
The fluoride, ThF 4 and its hydrate, the group. ThP4*4H 2 O, are very slightly soluble, as is also the potassium fluorothorate, K 2 ThF 6 -4H 2 O. Various hydrates of the
,
tetrachloride
may be crystallized from aqueous solution, provided that sufficient acid is present to prevent the
11]
469
precipitation of basic chlorides. Halides of lower oxidation states have not been prepared. The sulfide may be made by the action of sulfur or hydrogen sulfide upon the heated
not stable in water solutions. The 2 and Th 2 S 3 may be prepared by reducing 3 sulfides, ThS and ThS 2 with the metal. The former is a silvery semi-metallic substance which has been employed as a ceramic for use with highly electropositive metals. The anhydrous sulfate is very hygroscopic and forms hydrates containing 9, 8, 6, 4, and 2 moles of water. The nitrate, Th(NO 3 ) 4 -12H 2 O, may be crystallized from concentrated acid solutions, and the phosphate, Th 3 (PO4)4-4H 2 O, is formed as a gelatinous precipitate by adding sodium phosphate to a solution of a thorium salt. Both the nitrate and phosphate form many double salts, e.g., KTh(NO) 6 -9H 2 O and NaTh 2 (PO 4 ) 3
metal.
It is
Normal thorium carbonate has not been prepared, but a number of basic carbonates and complex carbonates are known, e.g., ThOC0 3 -2H 2 O and (NH 4 ) 2 Th(CO 3 ) 3 6H 2 O. The basic carbonates are soluble in excess ammonium
carbonate, carbonate.
probably
with
the
formation
,
The
iodate,
Th(IO 3 ) 4
is
complex but slightly soluble
of
and resembles the corresponding
eerie
compound.
In gravimetric analysis, thorium is usually precipitated as the hydroxide and weighed as the dioxide. The element
may be determined volumetrically by precipitation of the normal molybdate, followed by solution of compound in acid, the reduction of this molybdate in a Jones Reductor and the titration of the molybdenum from the + 3 to the
6 state.
PROTACTINIUM
11.
Occurrence.
is
stable isotope
As indicated in Table VI, the most Pa 231 which is a product of the chain,
,
U235_JVr h 23i( UY )_^Pa 231

years, the steady state
since
its half-life is
3.4
is
10 4
(about
amount of the 10~ gram per gram of U).

8
isotope
small
470
REFERENCE

TABLE
VI
ATOMIC NUMBER
91
[Ch.
XXII
PROTACTINIUM ISOTOPES.
Protactinium resembles tantalum in 5 oxidation state. the generally inert character of the The pentoxide, Pa 2 O B is somewhat more basic than the corresponding tantalum oxide and the freshly precipitated oxide dissolves in sulfuric acid, probably with the formation The element may be precipitated from the acid of PaO 2+ solution as a slightly soluble peroxyacid and as the phosThe pentachloride may be prepared by the rephate.
12.
Chemistry.
action,
Pa 2 O 5
5COC1 2 = 2PaCl 5
+ 5CO
2.
The
C.
opti-
mum temperature for the reaction is around 500
A few
milligrams of the metal have been prepared by the decomposition of the chloride on a heated tungsten filament. The metal is not readily oxidized by air. The oxide dissolves readily in HF and the fluoride resembles TaFs. 2 PaF 7 Salt, such as may be crystallized from a solution
in excess of
KF.
The very unstable uranium

brevium,
2,
Pa234m
also
called
be separated from its parent element, uranium Xi, by taking advantage of the difference in properties of thorium and tantalum. Thus, the mixture treated with hydrogen fluoride forms the slightly soluble
may
13]

while the uranium
471
UXiF
4,
goes into solution, doubtless

is
as the complex fluoride. by an isomeric transition.
Uranium Z
formed from
UX2
URANIUM
13.
Occurrence.
The average abundance
of
uranium
10~~ gram of in the igneous rocks is given as 4 per gram of rock, and in the earth's crust, as 0.0004 per cent. It is
estimated that the earth's crust to a depth of 20 kilometers contains approximately 1.3 X 10 14 tons of uranium. The principal ore is pitchblende or uranite, U 3 O 8 which is frequently associated with the rare earth oxides. Other ores are carnotite, KÔÛCVXÔs-nHÔ, calcium carnotite, CaO-2UO 3 -V 2 O 6 -nH 2 O, and autunite Ca(UO 2 ) 2 (PO 4 )2' 8H 2 O. Extensive deposits of uranite occur at Great Bear Lake, Canada, and in the Belgian Congo. Fairly extensive deposits of low grade carnotite are found in Colorado, Utah and Arizona. Most oil shales and calcium phosphate rocks run a few thousandth of a per cent of uranium. In view of the very great tonnage of such deposits, they constitute a
,
TABLE
URANIUM
ISOTOPES.
VII
ATOMIC NUMBER 92
472
REFERENCE
[Ch.
XXII
high potential source of the element. Uranium is frequently associated with gold and silver ores and the residues from smelters are another extensive source of low grade uranium
ores.
As may be noted in Table VII the long lived isotopes uranium have the mass numbers 238, 235, and 234.
,
of
14. Metallurgy. Pitchblende, U 3 O 8 may be roasted in with alkali carbonate in air or with nitrate to convert the The ore may then be treated with oxide to uranate. sulfuric or nitric acid to leach out the uranium as the
Purification of impure uranyl nitrate is uranyl salt. accomplished by extraction of the salt from a nitric acid The metal is prepared by the elecsolution into ether. trolysis of fused potassium uranium fluoride or by the reduction of the dioxide, chloride or fluoride, by calcium or
magnesium
in
a bomb.
With most reducing agents
it is
necessary to preheat the
bomb
to obtain the metal as a
massive product.
the boiling point
is
The
melting point of the metal is 1 130 C., 3500 C., and the density, 19.05 (a form).
The metal is slightly more electropositive than aluminum. The more important reactions of the metal are summarized
in
Table VIII.
TABLE
VIII
REACTIONS OF URANIUM
U 4- 3/2H = UH U + C = UC U + 2Si = USi U -f 2B = UB U -f l/2Ni = UN

2
2
2
C., also forms UC 2 Also forms U 6 Si, USi, U 2 Si 3 and USi3 Also forms UB 4 Rapid at 1300 C., also forms U 2 N8 and
,
Rapid at 250 C. Rapid at 800-1200
3U
-f
U+ U+ U -f U+ U+ U+ U+ U+ U+ U + UO 2 = 2UO
4P = U3 P O 2 - UO 2 S = US 2 2F 2 = UF 4 2C1 2 = UC1 4 2Br 2 = UBr 4 3/2I 2 = UI, 2H 2O = UO 2 + 2H 2 4HC1 = UC1 4 + 2H 2 2H 2SO 4 - U(SO 4 ) 2 -f- 2H 2
4
UN
Rapid at 700-1000 C. Also forms UzSz Also forms UF 5 and UF 6 Also forms UC1 5 and UC1 6
Also forms UI 4 Slowly with boiling water Rapid with cone, acid Very slow with tone, acid At 2400 C.
17)
473
reactors.
The only important use of the metal is in the nuclear The 235 isotope which is present in ordinary
of 0.71 per cent
is
uranium to the extent
the only naturally
occurring isotope fissionable (cf. XXIII) with slow neutrons. 15. Oxidation States. 2, 3, 4, Compounds of
2 state 6 oxidation states are known. The is highly unstable and few compounds such as US and UO 3 state, as, for example, are known. Compounds of the
5
and
+ +
UF
and UI 3 are stable as

,
solids
but
with the evolution of
2.
The
ions
U+3 reduces water U+4 and UO^ are
5 state, stable in aqueous solution but the ion of the H". The follow+4 and + into UO2~ 2 disproportionates
UO
ing potential diagram summarizes the energy relationship in acid solution:
IM
1.85
0.61
U+4
|
0.62
U
16.
U+
U0 + - 0.334
2
0.05
UO
2
|
++
The
3,
Compounds.
3
U+
resembles the rare earth
ions except for its strong reducing action.
The
halides
and UI 3 have been prepared. Compounds. The hydrated oxide, UO 2 -2H 2 O, precipitates when an alkali is added to a uranous solution. The anhydrous oxide may be formed by heating the hydrate, or by reduction of the uranous uranic
3,
UF UC1 UBr
17.
The
with hydrogen. This oxide is soluble in strong acids forming green solutions of uranous ion. UO 2 forms The series of solid solutions with both UO and UO 3 may be precipitated from uranous tetrafluoride, UF 4 The other tetrahalides are solution by fluoride ion. and the anhydrous chloride may be soluble, however, prepared along with some of the pentachloride by the
oxide,
3 8,
.
,
UO
action of chlorine
upon the metal, or CC1 4 upon
UO
3
8.
The
.
forms when the elements are heated together sulfide, 500 C. It is also formed by passing H 2 S over UC1 4 around The oxysulfide, DOS, may be prepared by the reaction UO 2 + H 2 S = UOS H 2 O.
2,
US
474
REFERENCE
[Ch.
XXII
6 Compounds. When uranium ores are 18. The extracted with a sulfuric nitric acid mixture, the oxide, is dissolved to form a yellow solution containing 3 O8
uranyl ion,
UO H
"
".
precipitate alkali pare from this uranate. It may, however, be prepared by the decomposition of uranyl nitrate. Upon heating, it forms U 3 Og, and The uranyl ion possibly at higher temperatures, U 2 O 5 forms slightly soluble compounds with phosphates, UO 2 HPO 4 2 O, UO 2 4 PO 4 arsenates, (UO 2 ) 3 (AsO 4 ) 2
.
3 trioxide, solution, as alkalies
The
UO
is difficult
to pre-
4H NH UO SO 4H O; complex alkali fluorides, K UO F sulfites, and sulfide, UO S. The sulfide is soluble in acid and in
;
ammonium
sulfate,
carbonate solution.
Uranyl halides, acetate,

fluorescence,
and are also subject to photochemical reduction by many organic compounds; for example, uranyl sulfate in sulfuric acid solution reduced by alcohol in the sunlight to uranous sulfate. The more common uranates are di-uranates, e.g., K 2 U 2 Or. They are not soluble in water, and precipitate when KOH is added to a UO 2++. The sodium salt, known as uranium is used in the manufacture of fluorescent uranium yellow, The uranates are glass, and also as a porcelain pigment. somewhat soluble in excess carbonate with the formation of carbonate complex ions such as UO 2 (CO 3 ) 2 Hydrogen peroxide forms, with uranyl nitrate solution, a precipitate of the peroxide, UO6*2H 2 O; and alkali peroxides form peroxy-uranates, e.g., Na2UO 2 4H 2 O. The hexafluoride, UF 6 may be prepared by the action
is
.
,
and nitrate are soluble. Uranyl salts show remarkable
of fluorine
upon the tetrafluoride. The pentafluoride is formed as an intermediate in the reaction, and the pressure of the volatile UF 6 in equilibrium with the UF 4 and UF 5 is 66mm at 215 C. The hexafluoride is used in the gas235 diffusion process for the separation of fluorides 2 F 9 and 4 Fn are also known.
from
238
.
The
The former is remarkable in that the crystal structure data show all of
21]
475
the uranium atoms to be equivalent. The hexachloride has been prepared but the bromide and iodide appear to be
unstable.
The uranyl ion gives a 19. Analytical. 2 2 Fe(CN) 6 cipitate with ferrocyanide,
K UO
4.
deep red pre.
It
be precipitated as
2
NH UO PO
4
may
also
The green
fluorescence of
for the quanti-
UO 4~f in ultraviolet light may be employed
tative estimations of small concentration of the ion. orange-red color of uranyl ion with sodium cresotate also be used for colorimetric determinations.
The
may
NEPTUNIUM
20. Isotopes.
Neptunium
(isotope 239)
was the
first
transuranium element to be discovered (1940). This 239 is the decay product of U formed by neutron isotope
238 It is highly important as the intermediate capture in U 239 from U 238 as carried out in the in the production of Pu step Hanford Plant, but because of its short life, it is not suitable for extensive studies on the chemistry of the element. 10 6 years and this However, Np 237 has a half-life of 2.2
.
isotope
is
available
in
weighable amounts through
its
production in the
by the
(n,
uranium-plutonium chain-reacting units, 238 237 to form reaction of fast neutrons on
2n reaction).
237
thus forms
Np
237
by
/3~
decay.
TABLE IX
NEPTUNIUM ISOTOPES. ATOMIC NUMBER
93
21. Chemistry.
The
oxidation states
+3, +4,
The
+5
and
6 are stable in aqueous solutions.
following
476
REFERENCE
[Ch.
XXII
potential
diagram summarizes the energy relations
in
values are the formal potentials for molal concentrations of the oxidized and reduced forms of the ions.
\M
HC1.
The
1.86
0.44
0.14
Np+
F
4
0.74
|
NpO
2
1.14
No
Np+ sip
"
-0.94 -0.67
is
NpO
'
++
As
indicated in this diagram, the metal tropositive and is readily oxidized to the
highly elec-
3 state.
43
"
The
is
+ Np(>2 couple is not readily reversible since it involves breaking the Np-O bonds but the NpO2+ NpO 2++ couple which involves only the transfer of a single electron is reversible. The oxidation of +4 4 requires a strong neptunol, NpC^ ", to neptunyl, NpO2 oxidizing agent. The neptunyl ion in acid is easily reduced 5 state. In spite of the unfavorable potential the to the
to
Np couple is reversible and Np " oxidized to Np" 4 by oxygen of the air. stable and not readily oxidized by air. It
1
+3
4" 4
Np
is
is
rapidly
The
4 state
slowly oxidized
NpO
by
nitric acid.
The Np+ 4
HC1 on platinum proceeds slowly at room with the evolution of volatile C1 2 This temperature reaction is rapid in hot solutions. The 3 ion has a pale purple color and in the solubility The chemistry of of its salts closely resembles La4"*" ". 44 4" 4 is similar to Th in most of the solubility relationships. Np The readily precipitated Np(OH) 4 has an olive green color. NpF 4 is slightly soluble and K^NpFe may be precipitated from a solution of KF and HF. All of the simple salts of NpC^4 appear to be soluble. The solubilities of the
reduction by
.
"
"
neptunyl salts are similar to those of uranyl
salts.
PLUTONIUM
22. Isotopes.
McMillan and Abelson

/3
in 1940 identified
Np
239
as the product of
produced from
238
which had been decay by a neutron capture. They estabof
239
23]
477
decay but were unable to 94 239 McMillan then bombarded uranium with deuterons hoping to produce another isotope of element 94 with a shorter half-life, and found definite evidence of alpha-activity. This investigation was continued by Wahl working with Seaborg and Kennedy, and the alpha-emitting isotope of element 94, produced by deuteron bombardment, was isolated and its chemistry studied. The new element was named plutonium after Pluto, the second planet beyond Uranus. The first isotope isolated proved to be Pu 238 and from the knowledge gained by a study of its chemistry, the 239 was isolated early in 1941. The tremendous isotope Pu importance of this isotope lies in its property of fission with slow neutrons and its ease of production in the carbonuranium chain reacting pile (cf. XXIII 16). Pu 239 the
lished the 2-3
day
half-life
by
ft
isolate the expected a-activity of the product isotope
longest lived plutonium isotope, has a half-life of only 24,000 years. It does not occur in nature except as a trace 14 (about one part in 10 ) in pitchblende where it is
continuously formed as the result of the absorption of neutrons (mostly from the spontaneous fission of U 235 ) by
uranium 238.
TABLE X
PLUTONIUM ISOTOPES. ATOMIC NUMBER 94
23. Chemistry. oxidation states
3,
Plutonium forms compounds in the +4, +5, and + 6. A semi-metallic
478
REFERENCE

known but
[Ch.
XXII
following potential diagram summarizes the oxidation-reduction potentials for the various couples. The values are for one molal solution of the ions in
2 oxide, unstable.
PuO,
is
this oxidation state is highly
The
1M HC1O
Pu
--4.
2.06
0.98
1.12
PuO 2+
0.93
Pu+3
Pu+4
-1.02
From these potentials, it is evident that plutonium resembles uranium in the highly electropositive character of the metal. With respect to the positive oxidation states, it is most remarkable that the energies of the three couples are so nearly the same. As a consequence, it is possible to have solutions which contain appreciable concentration of In fact, it is imall four oxidation states in equilibrium.
+4 and PuO + which do 2 possible to prepare solutions of Pu not contain some of the disproportionate products. The
5 state
is
ing reaction,
2PuO 2+
anism PuO 2+
somewhat unstable with respect to the followwhich is favored by a high concentration of H + The mech4H+ = Pu+ 4 + PuO 2++ + 2H 2 O
(1).
of the reaction appears to be the slow reaction:
2Pu+ 4 + 2H 2 O (2) coupled with " the rapid equilibrium: PuO 2+ + Pu+ 4 = PuO 2++ + Pu H h K = 8.5 (3). The disproportionate of Pu+4 is the reverse of reaction (2), and the equilibrium constant
Pu+ 3
+ 4H+ =
(Pu+
3
(Pu+ )(PuO 2+)

for the reaction in 0.5
M hydrochloric acid
+
is
170 at 25 C.
The direct reduction of + 6 plutonium to the + 5 state by reducing agents such as hydrogen peroxide, hydroxylamine, nitrous acid, silver and sulfur dioxides is fast while the reduction of the 4 state is slow. In fact, 5 to the the second step is generally slower than the disproportionation reaction (1). Likewise the oxidation of Pu+ 4 by many
27]
479
oxidizing agents appears to proceed through the disproportionation reaction

24.
The
3 State.
The hydroxide,
fluoride, oxalate,
phosphate and carbonate are

the hydroxide
is
"
slightly soluble.
However,
hydroxized.
color.
distinctly basic and the ion is not highly Pu 4 3 in aqueous solutions has a purple violet
4 State. Pu+4 has a green color and re+4 with sembles Th respect to the solubilities of its salts, the more important slightly soluble compounds being: the
25.
The
fluoride,
PuF 4 the potassium complex fluoride, 2 PuF6 the iodate, Pu(IO 3 )4, the phosphate, Pu 3 (PO 4 )2 and the +4 to basic carbonate. Hydrogen peroxide reduces Pu " 1 3 3 in the reverse Pu" and simultaneously oxidizes Pu" In sulfuric acid the steady state favors Pu4 4 reaction. 4 ion is complexed by hydrogen peroxide with and the
, ,
"
"
first of a brown complex containing two atoms and one peroxide and, at higher peroxide plutonium concentrations, a red complex with two plutonium atoms and two peroxides, possibly HO-Pu-O-OPu-OOH. At still
the formation
higher concentration of hydrogen peroxide, a slightly soluble plutonium peroxide is formed, whose composition 4 The depends upon the negative ion present. The hydroxide is not soluble in excess of OH"". tetrachloride is unstable with respect to the reaction
2PuCl 4 = 2PuCl 3
26.
discussed in Par. 24, PuO 2+ is unstable at high concentration of H+. The simple salts of the ion are all soluble. 6 State. 27. The PuC^4"* in acid solution is a much
C1 2
The
+
+
5 State.
As
H". In most other 2 stronger oxidizing agent than The respects the chemistry of the two ions is similar. addition of soluble hydroxides precipitates slightly soluble
UO
"
plutonates.
less
The
solubility of
barium plutonate
is
much
is
fairly soluble in
than that of sodium plutonate. sodium carbonate solutions.
The
latter salt
The more
480
REFERENCE
[Ch.
XXII
the
important slightly soluble salts of plutonyl ion are phosphate, arsenate and double sodium acetate
NaPuO 2 (CH CO
3
2 ) 3.
AMERICIUM
28. Isotopes.
The bombardment
of
238
by high energy
241
by particles (accelerated in a cyclotron) produces Pu the capture of the a particle and the emission of a neutron.
The Pu 241 gives Am 241 by ft d<ecay. U 238 O, n)Pu 241 The Am 241 has a half-life of about 500 Pu 241 JÂm 241
.
years and
is
the most stable of the six isotopes which are
now known.
TABLE XI
AMERICIUM ISOTOPES. ATOMIC NUMBER 95
29.
Chemistry.
The The
+3
oxidation
is
state
is
stable in
aqueous solution and
extremely
difficult
highly to
is pink. There is some evidence for the existence of the + 2 state, as tracer amounts of americium have been reduced by sodium amalgam and precipitated with BaSO 4 as a carrier. In this
oxidize or reduce.
color of the
Arn 1 3
"
americium appears to resemble europium, its The hydroxide homologue in the rare earth group. Am (OH) 3 has been oxidized by hypochlorite in 40 per cent
respect
in the
solution. The product (yellow in color) is soluble carbonate and is probably in the 5 state. The 4 hydroxide is doubtless formed as an soluble slightly intermediate in this oxidation. Very powerful oxidizing
2
K CO
agents appear to form
AmO
"
~f
in acid solution.
Both the
31]
481
6 states are unstable in acid solution with 4 and respect to the evolution of oxygen. The potentials of the VI couples are probably about IV and the 1.3 1.6 respectively in acid solution. All of the and 3
halides are
,
known and when

1
the fluoride
AmF
is
treated
with F 2 there is no oxidation. The chemistry of Am"4""^ resembles Eu" "^" with respect to the solubilities of its salts
in water.
CURIUM
30. Isotopes.
The curium
242
Table XII.
It is
Cm
isotopes are summarized in has a half-life of only about five months.

of
(a, n) reaction, and 241 absorbs a the action of neutrons on americium. by 242 which neutron to form the short-lived (18 hours)
,
made by a bombardment
Pu 239
Am Am
TABLE
XII
CURIUM ISOTOPES. ATOMIC NUMBER 96
gives
Cm
242
by
|8
decay.
In the short nuclear notation:

.
Am
Weighable amounts of (n, curium have been prepared by the second method. The 241 has not been prepared except longest lived isotope, Cm in tracer amounts. 31. Chemistry. Experiments with tracer amounts and with milligram quantities of curium, all seem to indialso
,
241
7)Am 'Am242 -^Cm242

242
cate that only

solutions.
Cm+3
3 oxidation state is stable in aqueous 3 ions of appear to resemble the
the rare earths with respect to the solubilities of its salts. One milligram of curium gives eight thousand billion 10 12 ) a particles per minute. Because of the enor(8
482
REFERENCE
[Ch.
XXIi
liberated by this a. radiation, studies on the of curium, except in tracer amounts, must be chemistry made by remote-control methods. In a water solution the
mous energy
a particles produce a tremendous number of electrons and positive

in the recombination considerable energy is libprocess, erated in the visible region of the ions,
and
spectrum.
This
phenomenon
is
shown
in Fig. 2.
BERKELIUM
32. An isotope of element number 97, berkelium, has been made 241 b J bombarding with alpha^
FIG. 2 Photograph of a curium solution in glass tube, taken by its own light, Picture courtesy Dr. G. T.
Am
The reaction (a, 2n) particles. 243 f orms Bk The new element is
.
an alpha-emitter with a hall-lite of 5 hours. The chemistry, as determined only with tracer amounts, appears to resemble that of curium but differs in that it is possible to oxidize berkelium to the + 4 state in 4 1.4 volts). This inaqueous solutions (Bk^-Bk^ ca creased stability of the + 4 state is in line with the similar situation which exists with respect to gadolinium and terbium and seems to indicate that curium has the 5f electron
structure.^
Seaborg.
...
CALIFORNIUM
33.
98,
The isotope, mass number 244 and atomic number has been made by bombarding Cm 242 with high energy
alpha-particles.
Cm
242
a = Cf 244
2n
This isotope is an a-emitter (E = 7.1 Mev) and has a half-life of 44 minutes. The separation of the newly formed element from the highly active target material is
33]

difficult,
483
extremely
but was accomplished by placing the sample, as hydroxide, on an ion-exchange column and The elution eluting with ammonium citrate solution. Because of the short process gave a clean-cut separation. half -life and small quantities prepared, a detailed study of the chemistry of the element is not easy, but the elution
curves
indicate
that
in
the
state
it
resembles
dysprosium.
Chapter XXIII
NUCLEAR REACTIONS
The ordinary chemistry of the concerned almost entirely with those atomic properties which depend upon the valence electrons, and the only significance of the atomic nucleus is its positive charge which determines the number of orbital electrons or the atomic number. In this chapter a brief discussion will be given of the properties of the nucleus and their relation to transmutation reactions. The radius of the nucleus increases from about 2 10~ 13 13 cm. for helium to about 8 X 10"" cm. for uranium. The relation of volume to mass is that which would be expected for the close packing of some fundamental mass particle. Moreover, it was early observed that the atomic weights of the lighter elements, Table I, with oxygen taken as 16, were very close to whole numbers which suggested that the nucleus was an aggregate of particles. The assumption was first made that the nucleus was a condensed system of
1.
The Atomic Nucleus.

is
elements
protons (hydrogen nuclei) and electrons. However, the discovery of the neutron (Par. 17) with approximately the mass of the protons and zero charge, has led to the more reasonable assumption that the nucleus consists of a close
Thus the 8 O 16 nucleus packing of protons and neutrons. may be thought of as eight protons and eight neutrons the mass number is thus 16 and the total positive charge or atomic number is 8. The decrease in mass (8 X 0.0089 8 X
:
0.0081
0.1360) represents the binding energy of the nu-
2]
NUCLEAR REACTIONS
particles.
8
485
10 20 ergs or 9.311 X 10 electron volts, this binding energy in 8 O 16 is 128 million electron volts. The reason that so many isotopes
clear
Since 1
gram equals
have atomic weights which are close to whole numbers arises through the fact that the mass contraction in the formation of the oxygen nucleus is an excellent mean value for a large number of elements.
TABLE
ATOMIC MASSES OF THE LIGHTER ELEMENTS

(These values are for O 16 = 16 instead of the chemial atomic weights which take the mixed oxygen isotopes = 16. The latter are obtained by dividing by
1,00023.)
For a given atomic number there is a Radioactivity. limited range of the neutron to proton ratio for which the
2.
nuclei are stable. This range is greater for the elements of even atomic number than for those of odd and as a result the even atomic numbers have a larger number of isotopes.
If
the ratio
is
radioactivity result.
outside the stable range, nuclear reactions or Thus if there is too large an excess of
neutrons, electron emission or beta-radiation occurs. It is not necessary to think of the electron as existing in the
486
REFERENCE
[Ch. XXIII
nucleus but rather that it is created by the conversion of a neutron into a proton, i.e., neutron equals proton plus electron. The loss of a beta-particle increases the atomic number by one and thus displaces the product to a periodic
The free group one higher than the parent element. neutron is a beta-emitter and its half-life is the order of 20 minutes.
on
If
1
proton
+ electron =
iH
too large an excess of protons, a number of may occur. With the heavier elements, an This particle is the helium alpha-particle is emitted.
there
is
reactions
(2
He
nucleus.
Since
it
has a charge of
+2
atom occupies a
position in the periodic system
the resulting two groups
TABLE
II
FUNDAMENTAL PARTICLES
lower than the parent. The alpha-particle is remarkably and in general the more abundant isotopes have mass numbers which are multiples of four, so it appears that the group of two protons and two neutrons must have some significance in the nuclear structure. Alpha-radioactivity
stable
often occurs with enormous energy, thus the a-particle from thorium C' has an energy of 10.5 million e.v. Another process which decreases the positive charge on
the nucleus
is the emission of a positron. This process is not known in the naturally occurring radioactive elements but frequently is observed in isotopes produced by bom-
2]
NUCLEAR REACTIONS.
487
The positron appears to be 18). (cf. Par. identical with the electron except for the opposite sign of The failure to observe the particle until the charge.
bardment
was due to its short life in the presence of electrons one positron and one electron react to form two photons or
recently
;
nihilation.
high energy (0.51 Mev) light rays with their mutual anThis process is reversible and the creation of a
Gamma
0.51
Mev
Gamma
Photon
CREATION
ANNIHILATION
FIG.
1.
Creation and annihilation of electron pairs.
when a photon with energy
positron-electron pair from a high energy photon may occur in excess of one Mev enters
the high positive field near an atomic nucleus. The probability of pair formation increases with the energy of the photon and the charge on the nucleus. A third method, K-capture, by which the positive charge on a nucleus may be reduced is the reverse of /3-radiation, that is, the capture of one of the inner orbital (K) electrons.
This process
to observe, but may be detected by emitted when another electron drops X-rays into the vacant K-orbital. It is known to happen in a number of the artificially produced radioactive isotopes and may be taking place in some of the so-called stable isotopes. The emission of particles from the nucleus is frequently
is difficult
means
of the
accompanied by very high energy light rays, gamma-rays, which have higher frequencies than the hardest X-rays.
488
REFERENCE

TABLE
III
[Ch. XXIII
TRANSFORMATION SERIES
UII
UY<
AcU
ThC
The
spectra of a-rays often show several discrete energy groups corresponding to different quantum levels of the product nucleus. In this case the excess of energy in the excited product nucleus is emitted in the form of 7-radiation. The j8-ray spectrum shows a continuous distribution of energy among the emitted electrons, terminating in
3]
NUCLEAR REACTIONS
f
489
a more or less sharp upper limit. Since the energies of the electrons from the nuclei are different but the energies of
the initial and final nuclei are presumably the same, the question of the conservation of energy in the process is The assumption is made that the difficult to answer. must be taken away by some new kind of particle energy This assumed particle is called still escaping observation.
x
the neutrino.
3.
The Transformation
Series.
Uranium and thorium
are unstable with respect to lead, and their disintegration occurs in a series of a- and /^-emissions, the so-called uranium series (starting with U 238 ) and the thorium series
corresponding end products are A third series also occurs ). in nature, the actinium series. However, this series does not originate with actinium but with AcU (U 235 ). The end 207 Some of the radioactive elements undergo product is Pb both a- and /^-disintegrations, thus causing forking in the
(starting with
Th 232 ). The
RaG
(Pb
206
and
ThD
(Pb
208
series.
series.
Table III gives the generic relations
in the three
The mass number
of the isotopes of the three series
be represented as follows; thorium series, 4n; uranium 1 series 2 actinium series, 4n + 3. The 4n 4n does not occur in nature but is now known from artificially 241 may be considered as the starting prepared isotopes. Pu point but the series is referred to as the neptunium series
may
series,
since
Np
237
is fairly
long lived (3
10 6 years).
Po 213
The
three natural series
may also be extended by the new
transuranium isotopes.
490
REFERENCE

96'
[Ch.
XXIH
4n series
Cm
24 0_
"94
Pu 236_
"92
u 232_
"90iTh
4n 4n
+ +
2 series
6Cm242 -
"94
P U 238_
"92
234
3 series
94
Pu 239 -
"92
U 235
The preparation of many new isotopes of all of the heavy elements has led to parallel series which differ by four mass numbers from the isotopes given above. 4. Other Natural Radioactivities. Radioactivity in naturally occuring isotopes of the
elements lighter than lead are
rare but a few cases are
known.
These are summarized
in
Table IV.
40 is important since it is the activity of 40 in the atmosphere. This activity principal source of also contributes an appreciable amount of heat to the
The
igneous rocks.
TABLE IV NATURAL RADIOACTIVE ISOTOPES OF THE HIGHER ELEMENTS
5.
Radioactive Constants.
The
rate of decomposition
is
usually expressed by the fraction, X, of a given quantity, Q, decomposed in a unit time, X = (l/(?) (dQ/di). The average life, 0, is 1/X, and the half period, T, i.e., the time required
for the transformation of
0.690.
one half of a given quantity, is one element is decomposing to form a second element, which in turn decomposes into a third element, the number of atoms of the first and second elements, Ni and The N2, when a steady state is reached, is: NiXi = N2X2
If
.
5]
NUCLEAR REACTIONS
491
velocity of the emitted rays is generally expressed relative to that of light, and their penetrating power in cm. of air,
aluminum, or
lead.
An
empirical relation of Geiger
and
4n+2
-15
4567
Log. E(Mev)
FIG. 2. The Geiger-Nuttall relationship. Logarithm of average life against logarithm of energy of alpha
particles.
life
Nuttall, Fig. 2, states that the logarithm of the average is inversely proportional to the logarithm of the
air for
range of the alpha-particle in

tion series.
a given transforma1(T 12 seer 1 and one

,
The value
of X for
Ra226
is
13.8
492
REFERENCE
[Ch. XXIII
21 gram of the element contains 2.6 X 10 atoms. Hence the number of disintegrations per second per gram is (13, 5 X
1CT 12 )(2.6
is
10 21 ) or 3.7
10 10
is
known
as the curie
and
This numerical quantity the standard unit of radio.
activity.
In 1919 Rutherford ob6. Artificial Disintegration. served that the fast RaC a-particles in passing through nitrogen gas occasionally (20 times per million a-particles) produced a new long range particle which was identified as
a proton. The mechanism of the process proved to be the nuclear reaction,
This experiment directed attention to the possibility of transmutation reactions and has led in recent years to the development of machines for producing beams of high speed particles, especially alpha-particles, protons and deuterons 2 (iH nuclei). The most important of these has been the cyclotron invented by Professor E. O. Lawrence. Hundreds of transmutation reactions have now been carried out. In some cases, as above, the product is a stable isotope, but more often the product is a highly unstable radioactive isotope and hundreds of these have now been discovered (cf. Table IV). The capture of the alpha-particle and the emission of a
proton, illustrated above for nitrogen and referred to as
<*>
(a,
p) reaction, occurs with

,
many
10
19
,
Ne
23
,
Mg
24
,
Mg
25
,
Mg
26
,
of the lighter elements: Al27 , Si 28 , P31 , and S32 .
7]
NUCLEAR REACTIONS
*
*
493
~""
j*
6 7 9 10 N 14 t 19 However, in some cases (e.g., Li Li Be Be 31 27 23 24 Na Mg Al and P ) the capture results in the emission This new particle had of the neutron, (a, n) reaction. because it produces no ionization along escaped detection Chadwick first deduced its presence from its its; path. to eject protons from material containing hydrogen. ability The neutron reacts with most nuclei and these reactions are considered below, Par 10. In addition to the (a, p) and (a, n) reactions discussed above, more complicated reactions occur with high energy Thus 400 Mev alpha-particles on lead alpha-particles. 203 with the emission of produces among other products Po 7 neutrons (a, 7n) reaction and the same beam on U 238 gives
,
,
with the emission of particles 19 units of mass and 6 units of charge. These high having energy reactions are called spallation (from the word "spall"
many
activities
such as
Ra 223
meaning "to
7.
splinter or crumble*').
Proton and Deuteron Transmutation. The proton and deuteron can penetrate the potential barrier of thfe positive nucleus much easier than the alpha-particle because The following are the more imof their smaller charge. of transmutation produced by bombardment portant types with moderately high energy protons:
20
N + Li + 5B + Be + C + Ca +
14
7 7
3
11
12
44
xH 1 iH xH 1 xH 1 xH 1 xH 1
1
= eC + 2 He4 - 2 2 He 4 = 3 2 He = Be + xD 2 = N + hv = 21 Sc44 + on
11
(p,
(p,
(p, (p,
a) a) 2a) d)
n)
13
(p, v)
(p,
The
first
,
of these reactions
is
also
shown by Li 6
is
14
,
F19
Na
23
and
39
.
The second
reaction
of interest in that
the process produced 17
Mev
Bombardment with deuterons

types of nuclear reactions:
7-rays. leads to the following
494
REFERENCE
[Ch. XXIII
The
first
reaction
is
is
important as a source of neutrons.
The
fourth reaction
to the
B 10
essentially the same, i.e., a proton is added nucleus and a neutron liberated and similar
,
, ,
Be 9 C 12 N 14 Na 23 Al 27 and many other nuclei. Reaction two results in the addition of a neutron to the nucleus and occurs also with Be 9 B 10 C 12 N 14 O 16 Na23 Al 27 and heavier elements. The formation of helium shown in the last equation is also given by Al 27
reactions are found with
,
, , ,
and many heavier elements. nucleus bombarded with deuterons

,
14
Frequently, a single will undergo all of the
common
example
:
nuclear reactions, as illustrated in the following

"
3oZn
30
64
Zn 63
29
Cu 63
Cu 64 62 29 Cu
29 28
Ni 61
+ on +2n + iH + tT + He
1
1 1
(d,
(d, (d,
4
n)
2n)
p)
(d, t) (d,
a)
Very high energy deuterons, such as the 195 Mev beam from the Berkeley accelerator, produces spallation similar When this beam to that discussed under a-reactions.
strikes a target, a reaction
known
as stripping also occurs
by which the proton is stripped from the deuteron and the neutron proceeds in a well defined beam with a peak energy of 90 Mev. 8. Tritium Reactions. When deuterium is bombarded
with tritium, the following reaction occurs:
iH 2
jH 3 =
He 4 +
in
is
The energy
liberated
by the
reaction
17.6
Mev.
reaction has a strong resonance effect at about 180
The Kev
9]
NUCLEAR REACTIONS
495
and at
this energy of tritium particles the efficiency is
number of reactions are known in greatly enhanced. which the action of tritium is the addition of two neutrons
to the
bombarded
46
nucleus,
e.g.,
Rh
103
xH =
3
96
Rh 105
iH 1
(t,
p).
Photon Induced Reactions. 100 Mev-photons produced by the betatron are capable of inducing numerous nuclear reactions such as (7, n), (7, a), (7, p), (7, np) and Photons with energies below 10 Mev are not (7, an).
9.
generally effective but the (7, n) reaction occurs in the 2 and Be 9 with the 2.6 Mev 7-ray from ThC". case of
10.
Neutron Reactions.
stripping
beam
Fast neutrons, such as the described above, or neutrons produced by
the action of a-particles on beryllium, can readily penetrate into the nucleus, and are very effective in producing dis-
The following equations illusintegrations by collision. trate the two most important nuclear reactions produced
13
13
AF + AF +
on on
1 1
= nNa 24 + He = Mg 27 + iH
2
i2
(n, (n,
a)
p)
The
reaction with the neutron capture and the helium emission is given by a large number of elements, some of the 14 O 16 F 19 Ne 20 P31 more important being Li 6 B 10 C 12
first
, ,
,
and Co 59 and the second type of reaction 28 24 Si P31 S 32 Ca 42 Cr52 Fe 56 and many of the by Mg heavier elements. There are also a few examples of neutron capture and deuteron emission (n, d) reaction, and also cases where a fast neutron appears to knock out another
Cl 35 Sc 45
,
Mn
55
2n) reaction. Since the neutron has approximately the same mass as the proton, elastic collisions with hydrogen atoms are very About effective in reducing the speed of fast neutrons. collisions suffice to slow down (or cool off) the fast twenty neutrons to the thermal energies of the hydrogen atom. Thus a few centimeters of water or paraffin at room tern(n,
neutron
496
REFERENCE
[Ch. XXIII
down from
perature placed in the path of fast neutrons will slow them several million volts to an average energy of 0.03 volt. These slow neutrons are readily captured by a
large number of nuclei forming isotopes with a mass one unit greater. As an example, thermal neutrons are captured
by hydrogen, forming deuterium.
The mean
life
of a
neutron in paraffin is only 1.7 X 10~ 4 seconds. From the data in Table I it is evident that the capture by H 1 results in a decrease in mass and this energy is emitted in the form
of 7-radiation, (n, 7) reaction. Among the more cases of neutron capture are those by C 12 Na 23
, ,
common
26
, ,
Si 30
Cl
,
25
,
K V
41
,
51
,
Mn
,
Mg
55
,
Cu
,
63
Sb 123
127
,
Ba 138 Hf 180 Au 197

,
Ga As75 Br81 Cd 113 Th 232 and U 238

69
, ,
,
Al 27 In 113
The most important neutron

induces nuclear fission and this
is
reaction
is
that which
discussed in the following
paragraph.
Nuclear Fission. The heavy nuclei, in addition to their instability with respect to a-emission, are also unstable with respect to splitting into two fragments. This
11.
process is called nuclear fission. The process results in a decrease in total mass of about 0.2 atomic weight units
which
is
roughly equivalent to 200 Mev.
FIG. 3.
Schematic representation of nuclear
fission.
The Bohr and Wheeler theory of fission pictures the nucleus as a drop whose surface has a high positive charge. A deformation of the drop results in strong repulsion of the two halves because of the charge.
The
fission is 5.9
excitation or deformation energy required to cause Mev for 238 and 5.3 Mev for 235 For the
somewhat
lighter elements the excitation energies are
12]
NUCLEAR REACTIONS
497
Whenever energies in excess of that required for larger. excitation are added, the probability of fission becomes Fission may be produced by bombardment with great.
high energy particles but the collision cross sections are very small and the chance of a single particle producing fission
correspondingly small. However, in the case of U binding energy liberated on the capture of a neutron
is
235
the
6.8
is
Mev
which
is
more than
sufficient for fission,
and since the
capture cross section for slow neutrons is very large, the 23S probability that a single slow neutron in a mass of U will cause fission becomes great. The tremendous importance of U 235 lies in the fact that it is the only naturally occurring isotope which does undergo fission with slow neutron capture. The reason that U 235 fissions with slow 238 does not, is the greater neutron binding neutrons, while U 236 This is in over that of U 239 in the product U energy
.
agreement with the general rule that binding energies are greater in nuclei with an even number of both protons and neutrons than they are in nuclei with an even number of
protons and an odd number of neutrons. Of the total 200 Mev fission energy, about 175
Mev
is
spent as kinetic energy of the fission fragments and the balance in the delayed emission of |8-particles and 7-rays
of the fission products.
12.
The Fission Products.

ranging in
The
fission
process
pro-
mass numbers from 72 to 158, duces fragments with peaks in abundance at 95 and 139, cf. Fig. 4. The newly formed atoms have neutron to proton ratio in excess
of the
This excess of for stability. reduced in a few cases by neutron emission but generally by a series of jS-disintegrations by which the neutrons are converted to protons. There are 64 known series or j8-chains involving a total of 170 different radioactive nuclides. The following is a typical example:
neutrons
is
number permitted
Xe140
(16s)
>Cs 140 (short) ^Ba 140 (12.8d) La 140 (40h) >Ce 140 (stable)
>
498
REFERENCE

have short
half-lives
[Ch. XXIII
Most
of the fission products
and the
total activity falls off rapidly as indicated in
Table V.
As the chain decays proceed, the abundance of the various nuclides will increase or decrease because of the differ-
10"
60
80
100
120
140
160
Mass Number
FIG. 4.
Fission products of
U 288
ences in half-lives, and the principal species contributing to the activity at various times are also given in
Table V. Prewar determinations gave 2.3 as the number of neuOver 99 per cent of the trons produced per fission of U 235 neutrons are emitted in the fission process (within 10~~ 12 seconds). The "delayed" neutrons are emitted by various fission products, and half-lives (in seconds) of 0.05, 1.5,
.
13]
NUCLEAR REACTIONS
499
TABLE V
GROSS FISSION PRODUCT ACTIVITY
(Values in disintegrations per minute per 10,000 fissions of U 235 by slow neutron capture for various times after fission)
4.5,
22 and 55.6 have been established.
The
last
two appear
to
come from Xe 137 and Kr87

13.
respectively.
Nuclear Chain Reactions. Since a single fission, caused by a neutron, produces more than one neutron, it is possible to set up a chain reaction. To accomplish this in a given mass, at least one of the neutrons emitted per fission must be captured and produce another fission. If the mass
is
small, the mean free path of the neutrons is large in comparison to the diameter of the mass and the per cent of
captures is small. As the total mass is increased the chance of capture increases and finally a mass is reached in which the rate of production and capture is unity. This is the critical mass required for the chain reaction. The problem in the construction of the atomic bomb was how to bring together two non-critical masses of pure fissionable material in the shortest possible time, so that the resulting mass
would produce an uncontrolled chain reaction.

14.
The Separation
of
236
.
The percentage
of
266
in
natural uranium is only 0.71 and the separation of the pure isotope was a major item in the atomic energy program. Two huge plants were constructed in Oak Ridge, Tennessee; one employed the principle of the mass-spectrograph and
500
REFERENCE
[Ch. XXIII
the other the differential rate of gas diffusion. The first 235 were obtained by the electroquantities of enriched
magnetic process, but the gas diffusion methods proved to be the most efficient. The gas, UF6 was allowed to diffuse through several thousand membranes with microscopic
,
holes and separation was attained by the higher velocities of the molecules with the lighter uranium atoms. 15. The Production of Pu239 . Two other nuclei, in addi235 tion to are known which undergo fission with slow ,
These are U 233 and Pu 239 Neither occur in nature but both are capable of large scale production, the
neutrons.
.
reactions being the following:
The
process has not been undertaken but the production of plutonium in the reactors at Hanford, Washington, in 1944 was one of the major acFission
+ n = Th U +n =U development of the U
Th 232
238
233
-^>Pa 233 -^>U 233
239
-A^Np 239 -^Pu 239
233
Product
Fission
Product
FIG.
5.
Diagrammatic representation of Hanford reactor.
complishments of the atomic energy program of World II. These reactors employ the fission of U 235 in natural uranium. Since U 235 concentration is low, the critical mass is many tons. Plutonium is made by the action of the "excess" neutrons on U238 In order to increase the chance
War
15]
NUCLEAR REACTIONS
501
of capture of the neutrons
by the
238
,
they are slowed
down by passage through graphite block (the moderator). The construction is essentially a giant cube of graphite
blocks with horizontal aluminum tubes running through the cube. The tubes contain the uranium in small cylinders
Concrete Shield
Graphite Moderator
Boron Steel
Control
Aluminum Tubes
Containing Uranium (Slugs)
Êlevator
Long; Graphite Holders
With Holes For Aluminum Tubes (For Production of Neutron Induced Isotopes)
FIG. 6.
Slow neutron reactor with graphite moderator.
(slugs)
and
the slugs.
also serve to carry the water required to cool The power level is controlled by vertical rods
containing boron which has a very high cross section for neutron capture. When the rods are completely in, the number of neutrons captured by the rods is sufficient to break the chain reaction. After the pile has run for some
502
REFERENCE
[Ch.
XXIh
uranium slugs are discharged, and allowed to "cool" in order for the fission product activity to decrease, The slugs are then dissolved and the plucf. Table V. tonium separated from the unused uranium and the fission
time, the
products by chemical methods.
The Hanford plant may be described 16. Power Piles. as a slow neutron heterogeneous reactor with graphite as a moderator. It is run at such a low temperature that it would be impossible to convert the energy liberated into
power, with appreciable efficiency. The amount of plutonium produced is less than the amount of U 235 consumed, that is, the breeding factor is less than one. If a similar 235 plant could be designed using fuel rods enriched with U 239 233 or U instead of natural uranium, in order to reduce Pu size and if materials for construction and cooling could the be found which would permit operation at 1000 C. and if the breeding ratio could be increased to one; it should be However the possible to produce power economically.
,
,
engineering problems are extremely difficult. The cost of the fission fuels, i.e., U 235 U 233 or Pu 239 is so great that they cannot be used as a source of cheap power unless the power
,
efficient breeder of additional fuel. If the new fuel produced could be fed back this attained, into the fuel rods and the only material consumed would
reactor
is
is
also
an
be U 238 (or Th 232 ). To operate a 100,000 kw power plant with 25 per cent conversion of heat to power would require 238 per year. only 300 Ibs of U Various other types of chain reactors have also been Thus a reactor employing a fast neutron constructed. chain reaction is in operation at Los Alamos, and a slow neutron heavy-water homogeneous reactor at the Argonne The latter reactor employs a solution of Laboratory. uranium in heavy water which acts as the moderator. Modification of these reactors may be developed for small power plants for military uses such as the propulsion of naval ships.
17]
NUCLEAR REACTIONS
503
17.
Cosmic Rays and Mesons.
The primary cosmic rays

amounts of
all the heavier Their energies average around 6 billion electron volts (Bev) although some may be considerably greater. There is no nuclear process which could give rise to such fantastic energies and it is presumed that the high
appear to be protons with smaller

nuclei.
velocities are attained

fields
which
exist
by the accelerating action of electric somewhere in space. The interaction of
the primary cosmic rays with nuclei in the atmosphere give showers of secondary rays consisting of protons, neutrons, The electrons, high-energy gamma rays and mesons. latter, also called mesatrons, are the latest addition to the Several types of mesons list of fundamental particles. have been recognized. The 7r-mesons have a mass 276
times that of the electron, and are both positive and They are found in the negative, and probably neutral. and have also been produced by bomupper atmosphere barding the light elements with 380 Mev alpha-particles.
They
are unstable (half-life ca 10~~ 8 seconds) with respect to decomposition into positive or negative /i-mesons which
have a mass 210 times that of the electron. The 7r-mesons have a half-life of 2.15 = 10~6 sec. forming a positron or electron and two neutrinos. The negative 7r-meson may
also be captured
of particles.
by a nucleus with the emission
of a
number
negative ju-meson also reacts with nuclei, probably converting a proton to a neutron. This reaction
The
Low has a low probability with the lighter elements. + 7r - and /^-mesons are not captured by nuclei beenergy cause of the repulsive forces. The ju-niesons form the bulk of the hard component of the cosmic rays and some penetrate hundreds of feet below the earth's surface. There is evidence for the existence of heavier V-particles with a mass several thousand times that of the electron.
The
total
number
of cosmic rays (secondary-rays) strikis
ing the earth's surface
approximately 2 per
cm 2
per
minute.
504
18.
REFERENCE
[Ch. XXIII
Radiation Health Hazards.
are destructive to living tissue.
penetrate only a few

is
mm
High energy radiations Alpha- and beta-particles of tissue before all of their energy
dissipated, largely by the liberation of free electrons. The effects of such radiations from an external source are
serious.
therefore localized on the skin, which, however, may be Taken internally, an alpha- or beta-emitter may
become fixed, as for example, radium becomes fixed in the bones by replacing calcium. Bone necrosis and cancer may result if the amount of radium retained is in excess of 0.1
microgram. X-rays and gamma-rays, since they are very penetrating, produce ion pairs along their entire path through the body. Radiation is measured in terms of its ionizing power and the 12 units, one roentgen, (symbol, r), will produce 1.6 X 10 The absorption within a few ion pairs per gram of air. of 500-1000 r of radiation by the whole body is fatal. days In the atomic energy program the permissible whole-body
radiation exposure
is
set at 0.1 r per day.
However,
in a
without serious The dosage received per day from cosmic rays is effects. 3 approximately 10~ r. The age of the sun appears to be 19. Solar Energy. around 3 billion years and to account for the enormous amount of energy radiated in that time it seems necessary to assume that it is supplied by nuclear reactions which use up hydrogen. The temperature of the interior of the sun is estimated at about 19 million degrees and at that temgeneral x-ray, a person
may
receive 40
perature the kinetic energies of the atoms are sufficiently large so that lighter nuclei are able to penetrate the repulsive barriers on collision.
Some energy
2
is
probably
contributed by the reaction
H + H = H + e+ + e+ + e~ = radiation
1 1
neutrino
which has a
total energy of 1.5
Mev. However the
rate of
19]
NUCLEAR REACTIONS
505
this reaction is
low and the following chain reactions have
been postulated as the probable source of most of the

energy,
C 12
+ H = N + radiation = C + e+ + neutrino N C + H+ = N + radiation N + H+ = O + radiation _ N + e+ + neutrino QIS N + H = C + He

1
13
13
13
13
14
14
15
i5
15
12
Net reaction
4H = He
1
energy
29 Mev.
the synthesis of helium from hydrogen, be regarded as the catalyst for the reaction. and carbon may The sun is approximately 30 per cent hydrogen and in order to produce the total energy radiated it is necessary to assume the 10-15 per cent of the original hydrogen has now been consumed.
net result
is
The
506
REFERENCE

TABLE
VI
[Ch. XXIII
SUMMARY OF ISOTOPES
Prepared from table by G. T. Seaborg and
I.
Perlman.
followed by abunSymbols: Naturally occurring isotopes indicated by dance in per cent; radioactive isotopes indicated by the type of radiaction, followed by value for half-life; 0~, emission of negative electron; + emission of positive electron; a, emission of a-particles; K, capture of ^-electron; I.T., isomeric transition; n, emission of neutron.
,
2 He 3 Li
4 Be
5
6
7
N 99.9844; 2, N 0.0156; 3, 0~ 12.1 yr. N 1.3 X 10~ 4, N 99.9999; 6, ft- 0.89 sec. 6, N 7.39; 7, N 92.61; 8, ft-, 2 a 0.88 sec. sec.; 9, N 100; 10, ftr 2.5 X 10 yr. 7, K 52 da.; 8, 2 a 10~ 10, N 18.83; 11, N 81.17; 12, 0~ 0.027 sec. 10, 0+ 20 sec. 11, 0+20.5 min.; 12, N 98.9; 13, N 1.1; 14,0- 5100 yr. 13, 0+ 9.93 min.; 14, N 99.62; 16, N 0.38; 16, ft- 7.35 sec.; 17, 0~
1,
4
3,
15
80
9
10
11
F Ne Na
12
Mg
99.757; 17, 0.039; 18, 0+ 126 sec.; 16, 29.4 sec. 100; 20, ftr 12 sec. 17, 0+ 70 sec.; 18, 0+ 112 min.; 19, 9.21 23, ft- 40 sec. 0.28; 22, 19, (3+ 20.3 sec.; 20, N, 90.51 21, 100; 24, pr 14.8 hr.; 25, 21, 0+ (?) 23 sec.; 22, 0+ 2.6 yr.; 23, ft- 58.2 sec. 78.6; 25, 10.11; 26, 23, 0+ 11.6 sec.; 24, 11.29; 27, ft- 10.2
n 4.14 sec. 14, 0+ 76.5
sec.; 15,
ft"
0.204; 19,
min.
13 Al 14 Si
100; 28, ft- 2.3 min.; 29, ft- 6.7 min. 25, ? 8 sec.; 26, 0+ 6 sec.; 27, 92.28; 29, 4.67; 30, 27, 0+ 4.9 sec.; 28, 3.05; 31, ft- 170 min. 100; 32, ft- 14.3 da.; 34, ftr 29, 0+ 4.6 sec.; 30, 0+ 2.5 min.; 31, 12 sec.
15
P
S
.
16
95.06; 33, 31, 0+ 2.6 sec.; 32, 0.016; 37, ft- 5.0 min. 36,
N 0.74;
N
34,
N 4.18; 35,
ft-
87.1 da.;
17 Cl
18
19
K
Ca
20
75.4; 36,0+ K, 0-2 33, 0+2.4 sec.; 34, 0+33 min.; 35, 10yr.; 24.6; 38, ft- 38.5 min.; 39, ft- 1 hr. 37, 34.1 da. 38, 35, 0+ 1.9 sec.; 36, 0.31; 37, 0.06; 39, ftr 4 min.; 99.63; 41, 0-1 10 min. 40, 87 0+ 1.3 sec.; 38, 0+ 7.7 min.; 39, 0.011 ftr 90% 93.3; 40, 10 yr.; 41, 6.7; 42, 0- 12.4 hr.; 43, 0- 22.4 hr.; 10% 1.8 44, 0- 18 min. + 39, ft 4.5 min.; 40, 96.96; 42, 0.15; 44, 2.06; 0.64; 43,
21 Sc
45, 0- 152 da.; 46, 0.0033; 47, 0~ 5.8 da.; 48, 0.19; 49, ftr 2.5 hr. 49, ft- 30 min. 3.92 hr.; 41, 0+ 0.87 sec.; 42, 0+ 3.92 hr.; 44, I.T. 2.44 da.; 44, 0+ 85 da.; 47, 0-3.4 da.; 48, 0-44 45, 100; 46% I.T. 20 sec.; 46,
;
N N
0-K
22 Ti
23
hr.; 49, 0~ 57 min. 43, ? 0.58 sec.; 45, 0+ 3.08 hr.; 46, 73.45; 7.75; 48, 7.95; 47, m 5.51; 60, 49, 5.34; 51 , 0- 6 min.; 51, 0- 72 da. 16 da.; 49, 600 da.; 51, 47, 0+ 33 min.; 48, 0+ 100; 52, 03.8 min.
24 Cr
49,*0'+
64,
41.9 min.; 50,
4.49; 51, 2.30; 66, ? 1.3 hr.
K 26.5 da.; 62, N 83.78; 53, N 9.43;
NUCLEAR REACTIONS
507
TABLE
25
VI
(Cont'd)
SUMMARY OF ISOTOPES
Mn
26 Fe
27
Co
28 Ni
29
Cu
30 Zn
31
Ga
Ge
32
33 As
34 Se
+ 51,0 46mm.;62%0M.T.21min.;52,0+K5.8da.;54,K310da. 66, N 100; 66, 0~ 2.59 hr. 62, 0+ 7.8 hr.; 63, 0+ 8.9 min.; 64, N 5.81; 66, K 0+ 4 yr.; 66, N 91.64; 67, N 2.21; 68, N 0.34; 59, 0- 46.3. + 18.2 hr.; 56, 0+ K 72 da.; 67, K 0+ 270 da.; 58, 0+ 15% 66, K 85% 72 da.; 59, N 100; 60, 0- 5.3 yr.; 60 m , I.T. ftr 10% 10.7 1.75 hr.; 62, 0- 13.8 min. min.; 61, 67, 0+ 36 hr.; 68, N 67.76; 69, K 5 X 10* yr.; 60, N 26.16; 61, N 1.25; 62, N 3.66; 63, 0- 300 yr.; 64, N 1.16; 65, 0- 2.6 hr.; 66, 0- 56 hr. 58, 0+ 7.9 min.; 59, 0+ 81 sec.; 60, 0+ 24.6 min.; 61, 0+ K 3.4 hr.; 62, 0+ 10.5 min.; 63, N 69.09; 64, K 0- 0+ 12.8 hr.; 65, N 30.91; 66, 0~ 5 min.; 67, 0" 56 hr. 62, K (?) 9.5 hr.; 63, 0+ 93% K 7% 38 min.; 64, N 48.89; 65, 0+ 1.3% K 98.7% 250 da.; 66, N 27.81; 67, N 4.07; 68, N 18.61; 69 m , I.T. 13.8 hr.; 69, 0- 57 min.; 70, N 0.62; 71, 0- 2.2 min.; 72, 0~ 49 hr. 64, 0+ 48 min.; 66, K 15 min.; 66, 0+ 9.4 hr.; 67, K 78.3 hr.; 68, 0+ 68 min.; 69, N 60.2; 70, 0~ 20.3 min.; 71, N 39.8; 72, 0~ 14.3 hr.; 73, 0- 5 hr. 66, ? 140 min.; 67, 0+ 23 min.; 68, K 250 da.; 70, N 20.55; 71, K 11 m 7 da.;71,0+39.7hr.;72 ,I.T. 5 X 10~ sec.; 72, N 27.37; 73, N 7.61; N 36.74; 75, 0- 89 min.; 76, N 7.67; 77, 0- 12 hr.; 77m 0~ 59 74, sec.; 78,0-2.1 hr. 71, 0+ 52 min.; 71, K 60 hr.; 72, 0+ 26 hr.; 73, K 90 da.; 74, 0~ 0+ 17.5 da.; 76, N 100; 76, 0~ 26.8 hr.; 77, 0- 40 hr.; 78, 0- 80 min. + 6.7 hr.; 74, N 0.87; 75, K e~ 127 71, 0+ 44 min.; 72, K 9.5 da.; 73,
35 Br
n 23.52; 80, 7.58; 77' , I.T. 17.5 sec.; 78, 9.02; 77, da.; 76, m 9.19; 83 , 0- 67 sec.; 49.82; 81, I.T. 59 min.; 81, 0- 17 min.; 82, 83, 0~ 25 min.; 84, 0" 2.5 min. 57.2 hr.; 78, 1.7 hr.; 76, 0+ 15.7 hr.; 77, 95% 0+ 75, 0+ 50.5; 80, I.T. 4.4 hr.; 80, 0- 0+ (3%) 18 min.; 0+ 6.4 min.; 79, 49.5; 82, 0~ 34 hr.; 83, 0- 2.4 hr.; 84, 0~ 30 min.; 86, 0- 3 81, min.; 87, 0- n 55.6 sec.; 87, 0- n 4.51 sec.; 88, 0~ 16 sec.
5%
36 Kr
77, 80,
87,
K 70% 0+ 30% 1.1 hr.; 78, N 0.342; 79, 0+ 2% K 98% 34 hr.; N 2.223; 81, I.T. ? 55 sec.; 82, N 11.50; 83, N 11.48; 83-, I.T. 113 min.; 84, N 57.02; 86, 0~ 4.5 hr.; 86, 0~ 9.4 yr.; 86, N 17.43;
37
Rb
38 Sr
*9
3 hr.; 89, 0~ 2.6 min.; 90, 0~ 33 sec.; 91, 0- 9.3 0- 74 min.; 88, fr 2.3 sec.; 93, 0~ 2.2 sec.; 94, 0- 1.4 sec.; 97, 0- short 19.5 da. 81, 0+ 5 hr. 82, 0+ 6.3 hr. 84, 0+ 40 da. 85, N 72.8; 86, l 87, N 27.2 0- 6.3 X 10 yr.; 88, 0- 17.5 min.; 89, 0- 15 min.; 90, short; 94, 0- short; 97, 0~ short. 0^ short; 91, 0" short; 93, m I.T. 70 min.; 85, K 65 da.; 86, N 9.86; 87m I.T. 84, N 0.56; 85 2.7 hr.; 87, N 7.02; 88, N 82.56; 89, 0~ 53 da.; 90, 0~ 25 yr.; 91, 0~ 9.7 hr.; 92, 0~ 2.7 hr.; 93, 0~ 7 min.; 94, 0~ 2 min.; 97, 0" short. 87 m I.T. 14 hr.; 87, K 80 hr.; 88, 0+ 2 hr.; 88, K 105 da.; 89, N 100; m 90, 0- 62 hr.; 91 , I.T. 51 min.; 91, 0- 57 da.; 92, 0- 3.5 hr.; 93, 010 hr.; 94, 0- 20 min.; 97, 0~ short.
sec.; 92,
; ;
;
508
REFERENCE

TABLE
VI
(Cont'd)
[Ch. XXIII
SUMMARY OF ISOTOPES
40 Zr
41
Nb
+ 4.5 min.; 89, ft 80.1 hr.; 90, 51.46; 91, 11.23; 89, I.T. or 2.80; 97, ft" 17.0 hr. 17.40; 96, ft- 65 da.; 96, 17.11; 94, 92, + 90, ft 15.6 hr.; 91, I.T. 62 da.; 92, ft" 10.1 da.; 92, ft" 21.6 hr.; m m 100; 93 , I.T. 42 da.; 94 , I.T. ft" 6.6 min.; 94, ? longer than 93,
N N
104 yr.; 96, I.T. 90 hr.; 95, 98, ft" 30 min.
ft"
35 da.; 96,
ft" 2.8
da.; 97, ft" 68 min.;
42
Mo
Tc
43
15.7; 96, 16.5; 9.12; 95, 15.86; 93, /3+ 6.7 hr.; 94, 9.62; 101, ft" 14.6 23.75; 99, ft" 67 hr.; 100, 9.45; 98, min.; 102, ft" 12 min.; 105, ft" short. + 4.5 min.; 93, ft+ 2.7 hr.; 94, I.T. 53 min.; 94, +, 65%, 92, 20 hr.; 96, 4.3 da.; 97, I.T. 90 56 da.; 95, 53 min.; 95,
92,
97,
N N
N N
<
44
Ru
45
Rh
10 6 ft" 2.7 da.; 99, I.T. 6 hr.; 99, ft" 9.4 1 min. 105, ft' short. 101, ft" 14 sec. ; 102, ft" + 2.8 da.; 98, 12.81 1.65 hr.; 96, 2.22; 99, 5.68; 97, 95, ft 31.34; 103, ft~ 42 da.; 104, 16.98; 102, 12.70; 101, 100, 18.27; 105, ft" 4.5 hr.; 106, ft" 1 yr.; 107, ft" 4 min. 4.3 da.; 102, ft + ft" 210 da.; 103, +, 19.4 hr.; 101, 100, ra 100.00; 103, I.T. 57 min.; 104 , I.T. 4.2 min.; 104, ft" 44 sec.;
da.; 97,
yr.
;
>
100 yr.; 98,

sec.
;
100,
ft"
80
<
46 Pd
47
Ag
105, ft" 36.5 hr.; 106, ft" 30 sec.; 107, ft" 24 min. 17 da.; 4 da.; 101, K, ft + 10%, 9 hr.; 102, 0.8; 103, 100, 27.2; 108, 26.8; 109, ft" 13 hr.; 22.6; 106, 9.3; 105, 104, 13.5; 111, ft" 26 min.; 112, ft" 21 hr. 110, in. 106, 45 da.; 106, ft + 24.5 min.; 106, 8.2 da.; 104, 0+ 73 51.35; 107, I.T. 44 sec.; 108, ft" 2.3 sec.; 109, I.T. 40.4 107, 225 da.; Ill, ft" 7.5 da.; 48.65; 110, ft" 24.2 sec.; 110, sec.; 109,
N N
N N
48
Cd
49 In
50 Sn
51
Sb
113, ft" 5.3 hr. + 33 6.7 hr.; 108, 1.21; 107, min.; 106, 0.88; 109, ft 330 da.; 110, 12.39; 111, I.T. 48.7 min.; Ill, 12.75; 112, m I.T. 2.3 min.; 12.26; 113 , 28.86; 115, 024.07; 113, 114, 2.33 da.; 115, ft" 43 da.; 116, 7.58; 117, ft" 170 min. + 6.5 + 2.7 da.; Ill, I.T. 20 hr.; 110, ft 65 min.; Ill, ft 109, min.; 112, 0+ 9 min.; 113, I.T. 105 min.; 113, 4.23; 114, I.T. 48 da.; 114, ft" 72 sec.; 115, I.T. 4.5 hr.; 115, 95.77; 116, ft" 13 sec.; 116, ft" 54.3 min.; 117, ft" 117 min. 0.61 115, 105 da.; 114, 0.90; 113, 0.35; 116, 14.07; 112, 23.98; 119, 8.62; 119, I.T. 13 da.; 120, 7.54; 118, 117, 33.03; 121, ft" 28 hr.; 121, ft" 36 min.; 121, ? ft" 130 da.; 121, ft" 28 hr.; 122, 4.78; 123, ft" 10 da.; 124, 6.11; 125, ft" 10 min.; 126, ft" 70 min. 2.8 hr.; 118, 39 hr.; 120, 5.1 hr.; 118, ft + 3.3 min.; 119, 117, + 17 6 da.; 121, ft min.; 120, 57.25; 122, I.T. 3.5 min.; 122, ft" 2.8 da.; 123, 42.75; 124, ft" 60 da.; 124, I.T. ft" 21 min.; 124, ft- I.T. 1.3 min.; 125, ft" 2.7 yr.; 126, ft" 60 min.; 127, ft" 93 10 min.; 134, ft~ hr.; 129, ft" 4.2 hr.; 132, ft" 5 min.; 133, ft"
K N
112, 105,
ft" 3.2 hr.;
N N
N N
N N
K N
<
<
52
10 min.
Te
117,
6 da.; 119, 0.091 121% 4.5 da.; 120, ?, ft+ 2.5 hr.; 118, I.T. 143 da.; 121, 17 da.; 122, 2.49; 123, 0.89; 124, 4.63; 7.01; 125, I.T. 60 da.; 126, 125, 18.72; 127% I.T. 90 da.;
NUCLEAR REACTIONS
509
TABLE
127, 130, 133, 124, 25.0
VI (Confd)
SUMMARY OF ISOTOPES
hr.; 128, 31.72; 129*, I.T. 32 da.; 129, pr 72 min.; m 25 min.; 132, pr 77 hr.; 34.46; 131 , I.T. 30 hr.; 131, pr 60 min. 134, pr 43 min. ; 135, pr < 2 min. 56 da.; 126, pr 13 da.; 127, 100; 128, pr 0+ 4.0 da.; 125, min.; 129, pr long; 130, pr 12.6 hr.; 131, pr 8.0 da.; 132, pr
fr 9.3
53
54
Xe
pr 22 hr.; 134, pr 54 min.; 135, pr 6.7 hr.; 136, pr 1.8 min.; 137, pr n 22 sec.; 138, pr 5.9 sec.; 139, pr 2.6 sec. 0.094; 126, 0.088; 127, I.T. 75 sec.; 127, I.T. 34 da.; 128, 124, 26.96; 133, 26.23; 130, 4.07; 131, 1.90; 129, 21.17; 132, m 10.54; 135, pr 9.2 hr,; 135 , I.T. 15.6 min.; 136, P~ 5.3 da.; 134, 8.95; 137, pr 3.8 min.; 138, pr 17 min.; 139, pr 41 sec.; 140, pr 16 sec.; 141, pr 1.7 sec.; 143, pr 1.3 sec.; 144, pr short; 145, pr
2.4 hr.; 133,
0.8 sec.
55 Cs
56
Ba
10.2 da.; 132, 7.1 da.; 133, 100; 134, 130, ? 30 min.; 131, 0- 3.15 hr.; 134, pr 2.3 yr.; 136, p~ 13.7 da.; 137, pr 37 yr.; 138, P~ 33 min.; 139, pr 9.7 min.; 140, pr 65 sec.; 141, pr short; 142, p- short; 143, pr short; 144, pr short; 145, pr short. m 12.0 da.; 132, 0.097; 133 , I.T. 38.8 hr.; 0.101; 131, 130, > 20 yr.; 134, 2.42; 135 m , I.T. 28.7 hr.; 136, 6.59; 136, 133, m 71.66; 139, 11.32; 138, 7.81"; 137 , I.T. 2.63 min.; 137, pr 84 min.; 140, pr 308 hr.; 141, pr 18 min.; 142, pr 6 min.; 143,
N K
57
La
58 Ce
59 Pr
60
Nd
< 1 min.; 144, pr short; 145, pr short. 19.5 hr.; 136, 0+ 2.1 hr.; 137, ? > 400 yr.; 138, 0.089; 135, 99.91; 140, pr 40.4 hr.; 141, pr 3.7 hr.; 142, pr 74 min.; 139, 143, pr 20 min.; 144, 0~ short; 146, pr short. 140 36 hr.; 138, 0.25; 139, 0.193; 137, 136, 0+ 16 hr.; 136, 11.07; 143, pr 33 hr.; 88.48; 141, p- 28 da.; 142, da.; 140, 144, pr 275 da.; 146, pr 1.8 hr.; 146, p~ 14.6 min. 100; 142, pr 19.3 hr.; 143, pr 13.8 da.; 144, 140, 0+ 3.5 min.; 141, pr 17.5 min.; 146, pr 4.5 hr.; 146, pr 24.6 min. 12.20; 27.13; 143, 97% 2.42 hr.; 142, 141, 0+ 3%, 17.18; 147, pr 11.0 da.; 148, 8.30; 146, 23.87; 146, 144, l 10 yr.; 151, pr 21 1.7 hr.; 150, 5.60; 150, pr 5 5.72; 149,
pr
K N
min.
61
Pm
Sm
Eu
62
63
200 da.; 147, pr 3.7 yr.; 148, pr 5.3 da.; 149, pr 47 hr.; 142, 151, pr 12 min. 13.84; 160, 7.47; 11.27; 149, 15.07; 148, 3.16; 147, 144, 10" yr.; 153, p- 47 hr.; 154, 26.63, a, 1 151, 0- 20 yr.; 152, 22.53; 155, pr 25 min.; 156, pr 10 hr. 47.77; 162, pr 9.2 hr.; 162, pr long; 153, 150, 0+ 27 hr.; 151, 20 yr.; 165, pr 2 yr.; 156, pr 15.4 da.; 157, 52.23; 164, pr
N
64
>
p-
15.4 hr.
Gd
Tb
65
14.78; 166, 155 da.; 164, 2.15; 156, 0.20; 163, 152, 21.79; 161, pr 18 hr.; 24.78; 160, 15.71; 158, 20.59; 157, 161, p- 4.5 min. 1 yr.; 169, 17.2 hr.; 155, 5.1 da.; 164, 0+ 4.5 hr.; 163, 162, 100; 160, pr 3.9 hr.; 160, pr 73.5 da.; 161, pr 420 da.; 161, p- 5.5 da.
510
REFERENCE

TABLE
VI
(Conl'd)
[Ch. XXIII
SUMMARY OF ISOTOPES
66
Dy
Ho
67
68 Er
+ 2.2 2.294; 161, min.; 158, 0.09; 160, 0.052; 167 (?), 156, m 24.97; 164, 28.18; 165 , I.T. 1.25 25.53; 163, 18.88; 162, min.; 165, 0" 145 min. 60 da.; 162 or 161, 20 min.; 161 or 162, 0+ 4.5 hr.; 160, 7 da.; 164, 0- 35 min.; 165, 100; 166, 0~ 27.0 hr. 163, 1.5; 165, 0+ 1.1 min.; 166, 32.9; 167, 24.4; 0.10; 164, 162, 14.2; 171, fr 7.5 hr.; 171, 26.9; 169, 0~ 9.4 da.; 170, 168,
K N
ft-
20 hr.
69
Tm
Yt
70
71
Lu
Hf
72
73
Ta
74
W
Re
100 da.; 169 , I.T. 10^ 9 da.; 167 (?), 7.7 hr.; 167, 166, 0+ m lO"6 sec.; 100; 170, ft- 127 da.; 170 , I.T. 2.5 sec.; 169, 171, 0- 500 da. 4.21 171, 33 da.; 170, 21.49; 14.26; 172, 0.06; 169, 168, 13.38; 177, 29.58; 175, 0- 99 hr.; 176, 17.02; 174, 173, 0- 2.4 hr. 100 da.; 175, 9 da.; 172 (?), (?) 0+ 2.15 da.; 171, 170, 10 10 yr.; 176 m ,0~3.67 hr.; 177, 0~ 6.8 da. 2.5 0-7.3 97.5 176, 70 da.; 176, 5.30; 177, 27.10; 18.47; 178, 0.18; 175, 174, 35.11; 181, 0- 46 da. 13.84; 180, 179, 8.2 hr.; 2.66 da.; 178 (?), 8.0 hr.; 177, 0- 16 da.; 180, 176, 10-* sec.; 181, 100; 182, 0- 117 da.; 182% I.T. 181, I.T. 2 0.40 sec.; 182, 0- 16.2 min. 140 da.; 182, 135 min.; 180, 179 or 178, 25.77; 0.122; 181, 29.17; 187, 14.24; 184, 30.68; 185, ftr 73.2 da.; 186 183,
N N
K
;
>
N N K
N K
0- 24.1
75
182,
hr.
64
hr.;
;
076 Os
K 50 da.
183 or 184,
185,
N 37.07
hr.
186,0- 92.8
186, 191,
13 hr.; 184 or 183, 80 da.; 184, 10* 62. 93 0-4 hr.; 187,
yr. ; 188,
0-18.9
184, 189,
N 0.018; N 16.1;
hr.
185, 190,
K 97 da.; N 26.4;
1.59; 187,
1.64; 188,
13.3;
0~ 15.0
,
da.; 192,
41.0; 193,
0- 32
77 Ir
190, 193, 191, 196, 198,
78 Pt
K 10.7 da.; 191, N 38.5; 192m LT. 1.5 min.; 192, 0- 70 da.; N 61.5; 194, 0- 19.0 hr. K 3 da.; 192, N 0.78; 193, K 4.33 da.; 194, N 32.8; 195, N 33.7; N 25.4; 196, I.T. 80 min.; 197, 0~ 18 hr.; 197, 0- 3.3 da.;
N
79
Au
80
Hg
81 Tl
7.23; 199, 0-31 min. or 0+ 1 da.; 192, 39.5 hr.; 4.7 hr.; 193, 15.8 hr.; 194, 191, m 185 da.; 196, 05.5 da.; 197, 100; 197 , I.T. 7.5 sec.; 195, 198, 0- 2.69 da.; 199, 0~ 3.3 da.; 200 or 202, 0- 48 min. 10~ 23 hr.; 197, 64 hr.; 198, I.T. 0.3 196, 0.15; 197 f sec.; 198, 10.1; 199, 17.0; 200, 23.3; 201, 13.2; 202, 29.6; 203, 0- 45.8 da.; 204, 6.7; 205, 0" 5.5 min. 1.8 hr.; 199, 27 hr.; 201, 75 hr.; 202, 7 hr.; 200, 198, 11.8 da.; 203, 29.1; 204, 0- 2.7 yr.; 206, 70.9; 208, 0~ 4.23
K K
N
K K
82
Pb
min.; 207, (AcC'), 0- 4.76 min.; 208, (ThC') 0- 3.1 min.; 209, 0- 2.2 min.; 210, (RaC) 0- 1J2 min. 499, K 1 hr.; 200, K 18 hr.; 201, K 8 hr.; 203, I.T. or K 52 hr.; 204, N 1.5; 204*, I.T. 68 min.; 206, N 23.6; 207, N 22.6; 208,
NUCLEAR REACTIONS
511
TABLE VI
(Cont'd)
SUMMARY OF ISOTOPES
hr.; 210 (RaD), pr 22 yr,; 211 (AcB), fir 36.1 min.; 212 (ThB), p- 10.6 hr.; 214, (RaB), p~ 26.8 min. 62 min.; 27 min.; 200, a, 197, a 2 min.; 198, a 9 min.; 199, a, 12 hr.; 206, 6.4 da.; 208, 100; 210 (RaE), short; 209, 204, p- 5 da.; 211 (AcC), a 99.68% p 0.32% 2.16 min.; 212 (ThC), 33.7% pr 66.3% 60.5 min. 213, pr 98% 2% 47 min. 214 (RaC), a 0,04% pr 99.96% 19.7 min. 90% a 10% 9 da.; 207, 5.7 203, a 40 min.; 205, a 4 hr.; 206, 5 X lO' 8 sec.; hr.; 203, a 3 yr.; 210, a. 138 da.; 211 (AcC'), 3 10~ 7 sec.; 213, a 4 212 (ThC'), 10-* sec.; 214 (RaC'), lO"4 sec.; 215 (AcA), a, pr 10-* 1.8 X lO"3 sec.; 216 1.5 (ThA), a, pr 0.014% 0.158 sec.; 218 (RaA), a 99.96% pr 0.04% 3.05 min. 8.3 hr.; 211, a 40% 60% 207, a 1.7 hr.; 208, a 4.5 hr.; 210, 1Q-* sec.; 216, a 7.5 hr.; 212, a 0.25 sec.; 214, a short; 215, 10~4 sec.; 217, a 0.018 sec.; 218, a. short. 3 3 216, a very short; 217, a 10~ sec.; 218, a 0.019 sec.; 219 (An), a 3.92 sec.; 220 (Tn), a 54.5 sec.; 222 (Rn) a 3.825 da.
N 52.3; 209, pr 3.32

K
83 Bi
84 Po
85 At
86
Rn
87 Fr
88 Ra
218, a very short; 219, a 0.02 sec.; 220, a 27.5 sec.; 221, a 4.8 min.; 223 (AcK) pr 21 min. 220, a short; 221, ct 31 sec.; 222, a 38 sec.; 223 *AcX), a 11.2 da.; 224 (ThX), a 3.64 da.; 225, pr 14.8 da.;'226, a 1622 yr.; 227, pr\
228 (MSThi), pr 6.7
yr.
Isotopes of elements 89-96 listed in Chapter XXII.
Glossary
The probability of absorption of an incident beam of radiation as it traverses some material. In the integrated form of the defining equation: (I = loe" ") where Io is the intensity of the impinging beam and I, the intensity of the beam after passing through thickness, x, u is the absorption coefficient. substance which gives Hydrogen ion in solution, or ACID. which neutralizes bases yielding water. In general, an acid is a molecule with a positive field which is capable of neutralizing a basic molecule having a "free" electron pair.
ABSORPTION COEFFICIENT.
1
ACTINIDES. The elements which contain 5/ electrons. ACTIVITY. Cf. Appendix IV. ALLOTROPY. The property shown by certain elements of being capable of existence in more than one form, due to differences in the arrangement of atoms or molecules. (See
Monotropic and Enantiotropic.) ALPHA-PARTICLES. Doubly charged helium atoms shot off during one type of radioactive change. AMPERE. Unit of electric current strength; one coulomb per second; the international ampere is the current which deposits 0.0011180 g. of silver per second. ANGSTROM UNIT. 10~ 10 meters; 10~8 cm. ANGULAR MOMENTUM. Product of the angular velocity and moment of inertia. The latter is analogous to the mass in 2 simple translation. Unit expressed in g. cm. /sec. acid or base). An oxide which when combined ANHYDRIDE (of with water gives an acid or base. ANODE. The electrode at which oxidation occurs. ATMOSPHERE. Unit of pressure. Defined as pressure exerted by a column of mercury 76 cm. high; 1.01325 X 10* dynes 2 per cm. 14.7 Ib. per sq. inch. ATOM. The unit particle of an element. A nucleus of definite integral positive charge surrounded by electrons.
;
513
514
GLOSSARY
The net positive charge on the nucleus of an atom; the ordinal number of an atom in the periodic
ATOMIC NUMBER.
system.
ATOMIC WEIGHT. Weight of an atom referred to the oxygen atom as 16,000, (chemical definition). The physical
atomic weights refer to O 16 = 16.000 and may be converted to chemical atomic weights by multiplying by the factor
1.00275.
AVOGADRO'S NUMBER.
6.0228
The number
of molecules in a mole;
10 23
AVOGADRO'S RULE. Equal volumes of all gases, at the same temperature and pressure, contain the same number of moleBAR.
cules (approximately). Unit of pressure;
10 6 dyne cm. 2
one atmosphere
1.013 bar.
BASE. A substance which gives hydroxide ion in solution, or which neutralizes acids, yielding water.
An easily oxidized element, as opposed to a noble element. BEV. Abbreviation for billion electron volts. BOILING POINT. The temperature at which the vapor pressure oi a liquid reaches standard atmospheric pressure.
BASE ELEMENT.
BRITISH THERMAL UNIT (BTU). Heat required to raise 1 Ib. of water 1 F. CALORIE. Unit of energy. Small calorie (denoted by cal.) is heat required to raise 1 g. of water 1 C. kcal. = 1000 1 cal. (15 C.) = 4.183 cal. Value varies with temperature.
joules.
CATALYST.
A substance which by its presence alters the rate of a reaction and itself remains unchanged at the end of the
reaction.
CATHODE.
The electrode at which reduction occurs. CATHODE RAYS. A stream of electrons. CENTIGRADE (C.). Temperature scale in which freezing
water
is
point of
called
and boiling point 100.

Emission of light during a chemical
CHEMILUMINESCENCE.
reaction.
COLLOID.
forces
become an important
phase dispersed to such a degree that the surface factor in determining its
properties.
COMPONENT.- One
of the minimum number of substances required to state the composition of all phases of a system.
GLOSSARY
CONCENTRATION.
515
The amount of a substance in weight, moles, or equivalents contained in unit volume.

Reciprocal of resistance.
CONDUCTANCE.
C = C A/L, where
atom
is
cross section, L, length,
and
COORDINATION NUMBER OF AN ATOM.
C, specific conductance. The number of atoms,

in
molecules, or radicals which are held about a central
relatively stable positions. COULOMB. The quantity of electricity transferred in one second by a current of one ampere; a coulomb can deposit
-
0.0011 180
g. of silver.
COVALENT BOND.
The term
frequently applied to an electron
pair bond, CRITICAL PRESSURE.

critical
The
pressure exerted
by a system
at its
temperature.
CRITICAL TEMPERATURE. The highest temperature at which a liquid and its vapor may coexist as distinct phases. CRITICAL VOLUME. The volume of unit mass at the critical temperature and pressure. CURIE. The amount of radon which can exist in a steady state,
"equilibrium," with 1 g. of radium. It is now used as a unit of the rate of disintegration of any radioactive substance and is defined as that quantity of substance which gives the
of disintegration as 1 g. of radium, 3.7 disintegrations per sec. DECOMPOSITION VOLTAGE. Cf. Appendix I.
same number
10 10
DEGREE OF FREEDOM.
The number
of the variables determining
the state of a system (usually pressure, temperature, and concentrations of the components) to which arbitrary values can be assigned. DEGREE OF IONIZATION. Cf. Appendix III.
DELIQUESCENT. The term applied to a salt which absorbs moisture from the atmosphere. DENSITY (volume-density). The mass per unit volume g. percc.
:
nucleus of the deuterium atom. An object of diamagnetic material will acquire a DIAMAGNETIC. magnetic moment opposite to the magnetic field. When a diamagnetic substance is placed in a magnetic field, the lines
DEUTERON.
The
(See Paramagnetic.) force between two point charges the distance r in a uniform medium is (e, 6) separated by / = et/kr* where k is called the dielectric constant. DIFFUSION LAW. The rates of diff usion of two gases are inversely
of force are spread out.
DIELECTRIC CONSTANT.
The
516
GLOSSARY
proportional to the square roots of the densities of the
gases.
DISTRIBUTION LAW.
A substance distributes itself between two immiscible solvents so that the ratio of its concentrations in the two solvents is approximately a constant (and equal to the ratio of the solubilities of the substance in each solvent). Requires modification if more than one molecular species is formed. DYNE. Unit of force. The force which will impart to a mass of
1 g.
an acceleration
of 1
cm. per
sec.
2
;
1 g.
980 dynes.
EFFLUENT.
Any solution which has passed through a bed of adsorbing material.
of negative electricity; 4.80239 X 10~ 10 electrostatic units. ELECTRON AFFINITY. The energy of attachment of an additional electron to a neutral atom. ELECTROPOSITIVE ELEMENT. An element that is readily oxidized, i.e., forms compounds of positive valence number, syn base element. ELEMENT. A substance composed entirely of atoms of the same
ELECTROMOTIVE FORCE. See Potential. ELECTRON. The unit charge or atom
atomic number. ELUATE. A solution of material removed from a solid adsorbent by a solvent (eluent). ENANTIOTROPIC. Crystal forms capable of existing in reversible
equilibrium with each other.
ENERGY. Work, or the capacity for doing work. ENTROPY. A measure of the irreversibility of a process; multiplied by the absolute temperature it is the energy required
to restore
to
its
a system which has changed from state original state. The property is extensive; for
it is
to
all
pure
EQUILIBRIUM, CHEMICAL. A state of affairs in which a chemical reaction and its reverse reaction are taking place at equal
velocities, so that the concentrations of reacting
crystals
zero at the absolute zero.
substances
remain constant.
EQUIVALENT amount
(1) Acid or base: the (g. equivalent weight). (weight) of substance necessary to give one mole of hydrogen' or hydroxyl, respectively, in a neutralization reaction; (2) oxidizing or reducing agent; a mole of substance divided by the number of electrons in the half reaction for the reduction of oxidation considered.
GLOSSARY
EQUILIBRIUM CONSTANT.
517
The product of the concentrations (or of the substances produced at equilibrium in a activities) chemical reaction divided by the product of concentrations of
power which
the reacting substances, each concentration raised to that is the coefficient of the substance in the chemi-
cal equation.
ERG.
Work done by a force
of
dyne acting through a distance
of one cm.
The term applied to a minimum in the freezing point-composition curve of a system. FAHRENHEIT. Temperature scale in which 32 denotes the freezing point and 212 the boiling point of water. FARAD. Capacity of a condenser which is charged to a potential
EUTECTIC.
of
1
volt
by
coulomb.
FARADAY.
96,501 international coulombs per gram equivalent; the charge of 1 mole (6.0228 X 10* ) of electrons; the amount of electricity required to precipitate one mole of a singly
The products formed by nuclear fission. FLUORESCENCE. The emission of light (other than reflected light) by a substance under illumination. FLUX. In metallurgy, a substance which will unite with some
FORCE.
of the reaction products to form an easily fusible magma. That which is capable of imparting acceleration to a
charged ion. FISSION PRODUCTS.
mass.
The net charge on an atom in a molecule, calculated by assuming that the electrons in a bonding pair are equally shared by the two atoms. FORMAL CONCENTRATION. Concentrations expressed as the
number of gram-formula weights per FORMAL POTENTIAL. The potential of a
concentration of
all
liter.
FORMAL CHARGE.
substances are
III.
reaction in which the formal.
FREE ENERGY.
GAMMA-RAY.
Cf.
Appendix
very high frequency light wave originating in the nucleus of an atom. ] GAS. A state of matter in which a given mass of a substance has neither definite size nor shape. GAS CONSTANT. The constant of the ideal gas equation relating volume, pressure, temperature, and mass (number of moles). = NRT. R = 8.3144 X 107 ergs per degree per mole; 0.082054 liter atmos. per degree per mole; 1.98719 cal. (15)
PV
per degree per mole.
518
GLOSSARY
GRAM.
of
1 cc.
unit of mass (or weight). of water at 4 C.
The mass (approximately)
GRAM
ATOM.
mass
in
grams numerically equal to the atomic
weight.
GRAM MOLECULE.
See Mole.
A mass in grams numerically equal
to the molecular weight of the substance in question. GRAVITATION CONSTANT. The standard acceleration of gravity,
980.665 cm/sec HEAT. A form of energy. HUMIDITY. The amount of water vapor per unit volume of
.
gas. Relative humidity is the ratio of the actual partial pressure of water vapor to the equilibrium pressure, water (liquid) to
water vapor, at the same temperature.
HYDRATED OXIDE. An oxide which compound with water.
precipitates as
a definite
HYDROLYSIS. A reaction involving the splitting of water into its ions, and the formation of a weak acid or base or both. HYDROUS OXIDE. An oxide which precipitates with an indefinite amount of adsorbed water. ION. -A charged atom or chemical radical. IONIZATION POTENTIAL. The potential required to transfer an electron from its normal quantum level to infinity. ISOBAR. One of several atoms having the same mass number but differing in atomic number. ISOMERISM. Existence of molecules having the same number and kinds of atoms but in different configurations. ISOMORPHOUS. Substances which have the same crystalline structures and are mutually soluble in the solid state. ISOTOPES. The term applied to atomic species having the same atomic number but different nuclear structure, as indicated by different atomic weight or different type of radioacUnit of energy = 107 ergs; work done per second in forcing 1 ampere through a resistance of 1 ohm. JOULE-THOMSON EFFECT. The temperature change in a gas when it expands without doing external work. KELVIN. Name applied to absolute-centigrade or thermodynamic temperature scale. KERNEL. The atomic nucleus plus all of the electrons except
JOULE.
KILO.
those in the valence shell. Prefix denoting 1000.
tivity.
LANTHANIDES. The elements from atomic number 57 to 71, formed bv the entrance of the 4f electrons.
GLOSSARY
LATENT HEAT.
519
The heat absorbed or evolved in an isothermal reversible process such as melting or vaporization. LATTICE ENERGY. The energy required to separate the ions of a crystal to an infinite distance from each other.
LITER. A unit of volume, 1000 cc. LOSCHMIDT'S NUMBER. Equivalent to Avogadro's number. MASS. Quantity of matter. Determined as the resistance offered by an object to a change of its motion, i.e., inertia. MASS LAW. See Equilibrium Constant. MEGA. Prefix meaning 1,000,000. MELTING POINT. The temperature at which a solid is in equilibrium with its liquid form (varies with pressure). MESON (also called mesatron). One of the fundamental particles, cf. Chapter XXIII.
METAL.
substance possessing so-called metallic properties,
i.e., electric conductivity, heat conductivity, high reflectivity, luster, etc., properties due to the high degree of freedom pos-
sessed
MEV. MHO.
by electrons of the substance. The abbreviation for million electron One reciprocal ohm.
Prefix denoting 10~ 6 = 10~ 6 meters (/*) Unit of length
.
volts.
MICRO. MICRON.
MILLI.
10~ 3
mm.
1
Prefix denoting 10~ 3
MOLAL.
Concentration expressed Concentration expressed
in
moles of solute per 1000 moles of solute per 1000
g.,
of solvent.
MOLAR.
in
cc.
of solution.
MOLE.
The weight of a substance in grams, numerically equal to its molecular weight; a "gram-molecule.'*
C. and
MOLECULAR VOLUME.
at
1
MOLECULAR
atoms
Volume occupied by one mole. 22.41151 atm. WEIGHT. The sum of the atomic weights of all the
of the molecule.
smallest physical unit of a substance. The moment about a point = force X perpendicular distance from point to line of force. MOMENT OF INERTIA. The sum of the products of each element of mass times the square of its distance from its axis of ro-
MOLECULE.
The
MOMENT
OF FORCE.
tation.
MOMENTUM.
MONOTROPIC.
NEUTRINO.
The product
The
of
Crystal forms one of which

particle
mass times velocity. is always metastable

is
with respect to the other.
whose existence
postulated to
ao
520
GLOSSARY
count for the apparent non-conservation of energy
ation.
in ^-radi-
NEUTRON.
zero
The elementary
particles of
atomic weight 1.009 and

of
1
chacflfee.
NORMAL
per
i.e.,
SOLUTION.
liter.
One having a concentration
equivalent
NUCLEON.
given to particles of mass number one, and neutrons. protons NUCLEUS. The positively charged center of the atom. The atom minus the orbital electrons. NUCLIDE. A species of atom having a given number of protons and neutrons in its nucleus. OCTET. The term applied to a group of eight electrons in the
The name
outer atomic shell.
OHM.
Unit of electrical resistance.
The
resistance of a uniform
g.
C. which has a mass of 14.4521 column of mercury at and a length of 106.300 cm. OHM-CENTIMETER. Unit of volume resistivity. A resistance
of
one
ohm
across a centimeter cube.

Cf.
OVERVOLTAGE.
OXIDATION.
Appendix
I.
number of an an atom or group of atoms. by OXIDATION STATE OR NUMBER. The charge on a simple ion or for a complex ion or molecule: the charge which is assumed on an atom to account for the number of electrons involved in the
increase in the oxidation state
An
clement; the loss of electrons
PARAMAGNETIC.
lines of
oxidation (or reduction) of the atom to the free element. An object of paramagnetic material will acquire a magnetic moment parallel to the magnetic field, and the
magnetic forro
wj)!
rnnvprg^j-nârd
it.
PASSIVE.
applied to the condition produced by treating certain metals with powerful oxidizing agents whereby the metal is rendered in effect more electronegative, e.g., iron treated with fuming nitric acid is rendered passive, and in this condition is not oxidized by silver nitrate solution as is
The term
PHASE.
non-passive iron. All of the homogeneous regions of a system which are of the same kind. PHASE RULE. In a system at equilibrium, the number of phases plus the number of degrees of freedom equals the number of components plus two.
PHOSPHORESCENCE.
nation.
Remission of light after previous illumi-
GLOSSARY
PHOTOELECTRIC EFFECT.
action of light.
521
The emission
of electrons under the
PHOTON. A "particle" of radiant energy. (E = hv.) PLANCK'S CONSTANT. The constant relating the energy and frequency of radiation. E = hv, h = 6.554 X IQ^êrg. sec. POLARIZATION (electrical). Refers to a distribution oTelectrical charges that gives rise to an external electric field. POLARIZATION (light). Light is said to be polarized which exhibits different properties in different directions at right angles to the line of propagation.
POLYMORPHISM.
forms.
The
ability to exist in
two or more
crystalline
POSITRON.
The
positive counterpart of the negative electron.
POTENTIAL (electric, gravitational, etc., at a point in a field). The work required to move a unit quantity (electron, gram,
from the standard position, or position of reference, to the point in question. POWER. The timerate of doing work, e.g., ergs per second. PRESSURE. Normal force per unit area. PROTON. The unit charge or atom of positive electricity; the nucleus of the hydrogen isotope of mass number one. QUANTUM NUMBER. One of the integers defining the energy of
etc.)
an atom. RADIOACTIVITY. Changes involving the partial disintegration of the atomic nucleus. Cf. Chapter XXII.
The opposite of oxidation; decrease in positive oxidation number; gain in number of electrons by an atom or group of atoms. REFRACTIVE INDEX. The ratio of the sine of the angle of incidence of a beam of light from a vacuum upon a substance to the sine of the angle of refraction, n = sin i/sin r. It is also the ratio of velocity of light in vacuum to that in the
REDUCTION.
medium.
REPLACEMENT
SERIES. The arrangement of the metals in order of the values of their oxidation potentials. RESISTANCE (electrical) R. Defined as the quotient of the pobetween two surfaces, divided by the resulting curtential rent 7, flowing from one to the other, as defined by Ohm's
,
law,
R = E/L
The
ROENTGEN.
2.083
produces quantity of radiation which 109 ion pairs per cc. of air. RYDBERG'S CONSTANT. A fundamental constant appearing in
522
GLOSSARY
the expression relating the terms of the hydrogen spectrum SOLUBILITY. The amount of solute (expressed in grams, moles etc.) present in a given amount (grams, moles, volume, etc.
of solvent or of solution at saturation.
SOLUBILITY PRODUCT.
of a solid strong electrolyte, e.g., for
is considered to be dissolved in the other, the solvent. The solvent is usuall) present in larger amount than the solute. SOLUTION. homogeneous mixture, the proportion of whose constituents may be varied within certain limits. Solutions may be either liquid, solid, or gaseous. SOLVENT. That constituent of a solution which is present ir
X (S-). SOLUTE. That constituent of a solution which A
The equilibrium constant for the solutior Cu 2S, K = (Cu+)
larger amount; or, the constituent which is liquid in the pun state, in the case of solutions of solids or gases in liquids. SPALLATION. An induced nuclear reaction in which an atom
ejects a large number of particles. SPECIFIC GRAVITY. The ratio of the mass of a certain volume of a substance to the mass of the same volume of a reference substance, generally water, for solids and liquids, and air for gases. The reference substance is at a specified temperature. SPECIFIC HEAT. The heat required to raise a unit mass (1 g.) of a substance 1 degree. SPECIFIC VOLUME. The volume of 1 gram of a substance. SPECTRUM. Light resolved into its component frequencies, as by a prism or diffraction grating. STANDARD CONDITIONS (of a gas). C. and one atmosphere, 01 760 mm. pressure. STANDARD POTENTIAL. Cf. Appendix I. STEPHAN'S CONSTANT. The constant relating total black body radiation and the absolute temperature. J = 0-r4 . o- = 5.672 X 10~6 erg per cm. 2 per sec. per deg.4 STOICHIOMETRIC. Pertaining to weight relations in chemical
reactions.
SURFACE TENSION.
;
The contractive force of a surface measured along unit length of its edge, usually expressed in dynes per cm. this is numerically equal to the work done in extend2 2 ing the surface 1 cm. in ergs per cm.
,
SYSTEM.
An
isolated
TEMPERATURE.
group of substances. The condition which determines whether heal
GLOSSARY
will flow to or
523
from one body to another.
See also Kelvin,
Centigrade.
THERMOELECTRIC FORCE.
of
The
two metal wires which

(in
arises
potential between the junctions when the two junctions are
at different temperatures.
TRIPLE POINT
one component system).
Temperature and
pressure at which three phases are in equilibrium, usually refers to liquid-solid-gas systems. VALENCE. The number of electron pair bonds which an atom
shares with other atoms. In inorganic chemistry the term is often used to mean oxidation state (cf. above). VAN DER WAALS' EQUATION. An equation relating the volume, pressure, and temperature of an imperfect gas in terms of = RT. two empirical constants. (P b) a/v*)(v VISCOSITY. The internal friction of a fluid; the reciprocal of
fluidity.
VOLT.
The
potential difference required to produce a current

joule
of one
WATT.
ampere through a resistance of one ohm. Unit of power, work performed at the rate of one
(of light).
per second.
WAVE LENGTH
Distance between consecutive corwave. Expressed in units of = 5890 length, Angstrom, microns, etc. Sodium yellow line = 589 X 10~6 mm. = 0.589 /*. A X-RAYS. High frequency light waves originating from the electrons of the kernel.
responding points in the light
Appendix
SUMMARY OF FUNDAMENTAL CONCEPTS

RELATING TO ELECTROLYTIC OXIDATION AND REDUCTION
(1)
An
electric current is carried

;
through a solution of an
elec-
by the motion of its ions the positive ions moving toward the cathode and the negative ions toward the anode. The current carried by each species of ion is proportional to its concentration and velocity.
trolyte
is transferred from the electrolyte to the electhe mechanism of electrode reactions, also called trodes through "half reactions/' which always involve the liberation of electrons at the anode and the using up of electrons at the cathode. The substances entering into either electrode reaction may be positive ions, negative ions, or neutral molecules. is the cell reaction. (3) The sum of the two electrode reactions If this reaction takes place spontaneously, we have a battery or electric cell capable of doing external work. If this reaction is not spontaneous, an external electromotive force must be used to force electricity through the cell and the process is called elec-
(2)
Electricity
trolysis.
The extent of the electrode reactions is to the total current that passes, and the passage of proportional one Faraday (96,500 coulombs) of electricity causes the electrode reaction to proceed to such an extent that one equivalent of each substance involved in the cell reaction is used up or produced.
(4)
Faraday Laws.
has the (5) At the cathode that reduction process occurs which highest oxidation potential; and at the anode that oxidation the process occurs which has the highest reduction potential, with that the speed of a given electrode reaction may be so exception slow that a reaction requiring a larger amount of free energy may 525
.
526
APPENDIX
first.
take place
tion potentials,
Use may be made of a table of oxidation-reducAppendix II, in order to predict the reaction that
should theoretically take place at each electrode. The potential of the cell reaction is the difference in potential of the two half reactions, e.g.,
Zn = Zn++ 2Ag = 2Ag+

Zn
(6)
+
H
2<r
0.7620 volt 0.7995 volt

1.5615 volts
2Ag+
= Zn++ + 2Ag
upon measurea solution is being electrolyzed with appreciable current, the potential required is greater than the reversible electrode potentials, due to irreversible changes taking place.
ments with very small currents. In general,
if
-êlectrolysis
The standard
potential values are based
-Eo(reversible)
4~
-îrreversible
The
may
irreversible potential required is known as overvoltage be traced to three general causes:
and
First.
The
If
potential necessary to overcome the resistance of the
solution.
a large current is flowing, the resistance of the elecincrease very markedly, due to the rapidity with which the ions are being used up in the immediate vicinity of the
Second.
trolyte
may
TABLE
OVERVOLTAGES, IN VOLTS, OF
HYDROGEN, OXYGEN, AND CHLORINE AT 25 C. CURRENT DENSITIES IN AMPERES PER CM. 2
SUMMARY OF FUNDAMENTAL CONCEPTS

electrodes.
polarization.
527
This effect
is
sometimes known as concentration
Third. Many of the electrode reactions are slow, and in order to get them to go with the speed required by large currents, additional potential or driving force must be used. This is especially true of gas reactions. These overvoltages depend not only upon the current density but also upon the nature of the results given in electrode, as is indicated by the
Table
I.
experimental Overvoltage decreases with increasing temperature.
TABLE
II
OVERVOLTAGES OF METAL IONS, VOLTS
Appendix
II
STANDARD OXIDATION-REDUCTION
POTENTIALS
VALUES, IN VOLTS, REFERRED TO THE HYDROGEN-HYDROGEN Ion COUPLE AS ZERO, ARE FOR UNIT ACTIVITIES AND TEMPERATURE OF 25 C. (Cf notes at end of table) Acid Solutions
.
59.8
STANDARD OXIDATION -REDUCTION POTENTIALS

Acid Solutions (Cont'd)
529
530
APPENDIX
II
Acid Solutions (Concltided)

Basic Solutions
531
COUPLE
E
3.03
2
COUPLE
Ca
4-
2OH- = Ca(OH) 2
= Te
4-20Sr 4-
HPO
+ 2030H4- 2H 2
1.14
20H- + 8H 2O = Sr(OH) 2 -8H O

2.99
2
= PO4
H-
4-20-
Ba
4- 8H O 4- 2OH~ = Ba(OH)-8H 2O
4-20La 4- 3OH- = La(OH) 3

4-
2.97
2.90
+ 20Mo + 6OH~ = MoO ~ + 4H O + 60Zn + 4NH = Zn(NH ++ + 20In + 3OH- = In(OH)

4
2 3 3)4
8
1.12
1.05
1.03
1.0
30-
Lu
+ 3OH- =
3042
Lu(OH)
H-
2.72
2OH= Mg(OH) + 202Be 4- 6OH~ = BejO~ 4- 3H O 4- 40Th 4- 40H- = Th(OH)
Mg
2.69
2.62
4-40Al 44-
2.48
2
4OH- = H AlOr
SO," + 2OH- = SO + H O + 20Se~ = Se + 20Sn + 30H- = HSn0 ~ + H O + 20Ge + 50H- = HGeO + 2H O + 40HSnO - + H O + 3OH4
2
0.93 0.92
0.91
0.9
HO
2
4-
20H- = H P0 2 ~
2
4- 30-
2.35
Fe
2.05
2
+ e~
B
4Si 4-
4OH- = H BO
2
H + 2OH- = 2H O
2
+ 20-
= Sn(OH) 6 + 20~ + 20H- - Fe(OH) 2
0.90
0.877
4-30-
6OH- =
SiO 3
1.79 1.70
4- 404- 3H 2 U(OH) 4 4- 2Na+ 442
4OH- = Na UO 4 4H O 4- 2e~ H PO - 4- 3OH= HPO 4- 2H O

2
1.61
4-20-
1.57
1.55
3
2OHMn(OH) 4- 20Cr 4- 3OH- = Cr(OH)

42
Mn
4- 30-
1.3
Zn
44-
20H- = Zn(OH) 2
= CdS
4-
4-20-
Cd Ga
4OH- = H GaO 3 " 4- H 2 O 4- 3e~ Zn 4- 4OH- = ZnO~ 4- 2H O 4- 20Cr 4- 40H- = CrO 2 4- H 2 O 4- 306V 4- 33OH- = 16H 2O
-f
2
2
S~
20-
1.245 1.24
1.22
1.216
1.2
4-
HV Oi7
6
4-
300-
1.15
+ 20+ 2OH- = Cd(OH) + 20Co + 20H- - Co(OH) + 20Ni + 2OH- = Ni(OH) + 20AsO - + 4OH= AsO + 2H O + 20Sb0 Sb + 40H+ 2H + 30- As + 4OH- = As0 + 2H O + 30ReO + 4OH- = ReO + 2H O + 30- Re + 8OHReO + 4H O + 70ReO Re + 4OH+ H O + 40Te + 6OH- - TeO + 3H O + 40Fe(OH) + OH= Fe(OH) + g~
Cd
2 2
0.828
0.809
0.73
0.72
0.67 0.64
0.68 0.594
=='
==
0.584
0.576
0.57
0.56
532
APPENDIX
II
Basic Solutions (Concluded)
STANDARD OXIDATION - REDUCTION POTENTIALS
533
NOTES ON THE USE OF THE TABLE OF OXIDATION- REDUCTION

POTENTIALS
The above table of important oxidation-reduction potentials has been prepared for ready reference. Additional values for couples less frequently employed will be found under the various
elements.
The
values for couples involving
\M H+
have been given
in the first part of the table and those for couples involving in the second part. The potential of many couples is indeand although these have been included in the pendent of
1M
OH~
pH
table for acidic reactions, they might have been repeated for the
latter table.
The couples are arranged in order of increasing oxidizing power, that is, the oxidized form of any couple has sufficient energy to oxidize the reduced form of any couple of higher positive potential. The convention regarding the sign of the Q values is that used throughout the text. The couple is written with the electrons on the right side and the sign is positive if the reduced form of the couple (written on left side) is a better reducing agent than H2. The values, which are referred to the potential of the hydrogenhydrogen ion couple as zero, are for 25 C. and all gas pressures, 1 atmosphere, and all activities (Append. IV), 1 molal, unless otherwise stated. The potential at other concentrations and pressures at 25 C. is given by the expression
where Q is the product of the activities (solutes in moles per liter and gases in atmospheres) of the products divided by the product
of the activities of the reacting substances, each activity raised to that power whose exponent is the coefficient of the substance in the half reaction, and n is the number of moles of electrons involved in the half reaction as written. Activities of pure solids and liquids are taken as unity.
Example:
2C1-(1AO
2Cl-(0.01JkO
= -
C1 2 (1 atm.)
Cl(5atm.)
+ +
2er;
-E=
E>
1.358
2<r;
log
E = -
1.358
0.138
- -
1.496
534
APPENDIX
tl
These potential values merely represent the difference in energies of the products and the reacting substances and as such give no information as to the speed of the reaction; indeed the mechanism of the reaction may be such that it cannot take place " in spite of a favorable potential value. Thus, Fe = Fe + + Ze~\ + 0.04 volt, indicates that H+ would oxidize iron to the ferric + state, but the mechanism of the reaction is Fe = Fe+ + 2^~, = Fe+++ + e~, + 0.44 volt, and Fe++ 0.77 volt, and H+ cannot bring about
" "
l
the second step. In general it may be stated that many of the reactions given are not capable of
-0.2
-0.4
experimental attainment under equilibrium conditions for one of two reasons: (1) the reaction is slow, as, for example, the reduction of sulfuric acid to sulfurous acid in dilute solutions, or the evolution
of hydrogen
-0.6 -0.8
-1.0
-1.2
1.4
FIG. 1. Change of concentration of
E with H4
".
on zinc which may require an overvoltage of 1.2 volts; or (2) the final and initial substances cannot exist together because of an intermediate Fe" "^ state, as for example, the Fe which gives Fe+ + or Cl~ + HUO couple = HC1O + H+ + 2e~, which would give C1 2 at 1M H+. Two half reactions may be added or
1
subtracted to give a third half reaction but the potential of the third reaction is
derived
by the addition or subtraction oj the free energies (Append. Ill) and not by the addition of the potential values. However, if two half reactions are subtracted to give a complete reaction, the potential of the reaction is the difference in the potentials of the two couples. The change in the half reaction-potentials with change in H" concentration for a number of couples is shown graphically in Fig. 1. The various couples given in the figure are as follows:
1
"
A JH = H+ + e~ A' $H + OH- = H O + e~ B Br- + Ag = AgBr + e~ C Fe++ = Fe+++ + e~ C' OH- + Fe(OH), = Fe(OH) +
2 2 2
3
f~
535
D 2H O + NO = NO - + 4H+ + 3e~ D' 4OH- + NO = NO - + 2H O + 3e~ E H O = iO + 2H+ + 2e~ E' 2OH- = |0 + H O + 2<r F N O + 3H O = 2HNO + 4H+ + 4e~ ~ F' N O + 6OH- = 2NO + 3H O + 4e~
2 3 3
2
Potential diagrams are convenient for summarizing energy relationships between the various oxidation states of an element. Thus in the following illustration,
M
I
0.9
1.1
M++
I
0.5
M+
3
0.9
M+
1.0
MO,,
the numerical values are E potentials for the couples involving the oxidation state to the left (reducing agent) and to the right
(oxidizing agent), e.g.,
M+ + 2H O = MO + 4H+ +
3
er
E = -
0.9 volts
In the above illustration the
M M + couple
The
is less
1 state is unstable, since the +-M"f+ positive than the couple.
2M+ =
M + M++
E =
0.2 volts.
and
+
,
proportionation reactions. + oxidized by
3 states are stable with respect to similar disThe metal and M"*" should be readily
M+
M++
2M++
The
2
2H+ = M++
3
+H
2
E =
1.0 volt.
should be oxidized by atmospheric oxygen.
+ O + 2H+ = 2M+ + H O
H
E = =
0.5
- (-
0.68)
0.18 volt
3 3 state should not be oxidized by O 2 since the 2 8 However 2 O 2-O 2 couple. couple is more negative than the even in H+, should be oxidized by strong oxidizing agents such as chlorine.
M+ -MO M+
\M
2M+3
+ C1 + 4H O = 2MO +
2
2
2C1~
8H^
E = -
0.9
- (-
1.36)
0.46 volt.
Appendix
III
FREE
ENERGY VALUES AND THEIR USE
Summary of concepts relating to free energy data, and their use in predicting the direction and extent to which a given reaction
will
proceed:
energy of a process is the maximum available obtainable in going from the initial to the final state. The free energy change, AF, of a chemical reaction is the free energies of formation (from their elements) of the products of the reaction, less the free energy of formation of the reacting sub(1)
The
free
is
Work which
stances.
Example:
^CaO
CaO
2HC1 = CaCl 2
+ H O; AF =
2
FCa ci
^HjO
2/*HCl-
(2) The free energy values for the substances in Table I refer to energy of formation from the elements at 25 in their standard states or states of unit activity, which are pure solid, pure liquid, gas at one atmosphere, and solute at 1 molal activity. The free energy of a reaction, in which all the substances are at unit activ-
ity and at temperature T, is designated as AFT. The free energies of all elements and of H+ are taken as zero in their standard
states.
(3) The relation between the free energy change for substances in their standard states and the equilibrium constant, K, is
,
- RTlnJC = AF T or - 1364 log X = AF 298 K (in cal.) where R is the gas constant and T the absolute temperature. The
10
o
more general
where
relation
is
- RTlnK/Q = AFT
Q has the same form as the equilibrium constant, but the concentrations refer to the values of the substances in their initial and final states. If these are unity, then Q is unity and the free
energy
is
AF.
Example:
âction:
We may
Cl 2(aq
.)
+HO
2
calculate the equilibrium constant for the

(i
iq .)
= H+ +
Cl~
+ HClO (8oU
from
536
FREE
ENERGY VALUES AND

Hence
THEIR USE
537
logio^C = 4600/1364; 10- 4 (4) It follows from this relation that a large negative value or that the reaction as written for AF means a large value for is capable of proceeding to practical completion. It must be emphasized again, however, that free energies give no information as to the speed of the reaction. (5) The reversible electromotive force, E, is a direct measure of the maximum available work or free energy of a chemical AT? where n is the number of Farareaction: n* 23066. jE = of electricity which flow through the circuit, and AF is days
the
value AF 298 = 4600. (H+)(Cl-)(HC10)/(Cli)
4.3
given in calories.
Example: Ag+
JH 2 = H+
0.7995
+ Ag;
,
0.7995.
AF = -
X 23066 = -
18440
cal.
Since the free energies of H2, H + and Ag are zero by definition, F298 of Ag+ is 18440. Example: To calculate the solubility product of AgCl at 25 C.
Ag + Cl- = AgCl + Ag = Ag+ + er Ag+ + Cl- = AgCl

Hence
e~
0.2222 volt " 0.7995 0.5773 volt
0.5773
23066
1365 log
l/K,
and
1.8
10-
10
TABLE OF STANDARD FREE ENERGIES OF FORMATION AT 25 C.
many positive ions which may be calculated directly from the oxidation-reduction potentials have not been included, cf. Ag + P. (5) above.
Values for
,
538
APPENDIX
111
TABLE OF STANDARD FREE ENERGIES
(Cont'd)
FREE
ENERGY VALUES
AND
THEIR USE
539
(Cont'd)
540
APPENDIX
til
(Cont'd)
Appendix IV
IONIZATION OF STRONG ELECTROLYTES

freezing point lowering of a molal solution of a strong electrolyte such as sodium chloride is somewhat less than twice
The
the molal freezing point lowering (cf. Hildebrand, Prin. of Chem., p. 59) and the assumption was formerly made that the sodium chloride was only partially ionized. It is now believed that the sodium chloride is completely ionized in the sense that
TABLE
ACTIVITY COEFFICIENT OF TYPICAL ELECTROLYTES AT 25
C.
the ions are capable of independent motion, and that the apparent non-ionization is due to the forces acting between an ion and its neighbors in general rather than its attachment to any particular ion. Since this force causes a departure of the ions from the behavior of perfect solutions, it is necessary to use a corrected con541
542
APPENDIX IV
centration, called activity, a, in all thermodynamic relations, and the ratio of the activity to the concentration (molality) is defined as the activity coefficient, 7 = a/c. At infinite dilution the force between the ions is zero, and the activity equals the concentration,
i.e.,
7 =
1 (Fig. 1).
As
the concentration increases, the activity
1.2
1.1
i.o
0.9
0.8
NaCI
fl.7
0.6
KBr
0.6
KCI
0.4
0.3
0.6
0.9
1.2
1.6
Square Root of Molality
FIG.
1.
Activity coefficient of hydrogen and alkali halides.
becomes less than unity, due to the attraction of the oppositely charged ions (Debye and Hiickel theory), but at high concentrations other factors enter such as the force of repulsion between the large hydrated ions, or the change in hydration of the ions, and the coefficient may become greater than unity. It is not possible to measure the activity of an ion of one sign
coefficient
IONIZATION OF STRONG ELECTROLYTES
543
independent of the ion of opposite sign, i.e., Na+ is not independent of Cl~ in NaCl; hence the activity is determined as the mean of both ions, and the activity coefficient expressed as the mean activity divided by the mean molality. The mean activity and molality are defined in such a manner (cf. Lewis and Randall,
Thermodynamics, p. 328) that the ratio finite dilution for all types of salts.
approaches unity at
in-
Appendix
CRYSTAL FORMS AND TYPES OF CRYSTAL LATTICE

which
according to the elements of symmetry is determined by the following operations required to bring the crystal into coincidence with its
crystal
it
is classified
possesses.
Symmetry
original position.
(a)
an axis through
Rotation about an Axis. If a crystal can be revolved about its center so that similar faces recur n times in one
Only axes
rotation, it is said to possess n fold symmetry about this axis. of two-, three-, four-, and six-fold symmetry are known
or in fact are possible with a system of particles at finite distances apart. (b) Reflection in a Plane. crystal which may be divided by a plane into two parts, mirror images of each other, is said to
possess
(c)
symmetry about
this plane.
Inversion about the Center. If every line drawn through the center cuts similar parallel faces on opposite sides of the center, the crystal is said to possess a center of symmetry. If a crystal can (d) Simultaneous Rotation and Reflection. be revolved about an axis so that n times in one rotation faces recur which are alternate mirror images, the crystal is said to
possess an axis of composite symmetry. Only four- and six-fold axes of composite symmetry can occur. Crystal Classes. There are 31 possible combinations of these four types of symmetry and these, together with the crystal with-
out any symmetry, constitute the 32 crystal types. The 32 types are grouped into six crystal systems with the
following characteristics: This system includes all crystals (1) Isometric or Cubic. having three interchangeable axes at right angles. All crystals have 4 axes of three-fold symmetry. One of the most important
544
CRYSTAL FORMS
forms
is
AND
TYPES
OF CRYSTAL LATTICE
545
the cube which has 3 axes of four-fold symmetry, 4 axes
symmetry which also have six-fold composite symmetry, 6 axes of two-fold symmetry, nine planes of symmetry and a center of symmetry. Other forms are the octahedron, doof three-fold
decahedron, and tetrahedron. One four-fold axis (may be four-fold com(2) Tetragonal. axis) and two interchangeable axes at right angles to the posite principal axis and to each other. The tetragonal prism is a common form.
One three-fold or six-fold axis of symmetry. (3) Hexagonal. Three interchangeable lateral axes of reference are generally employed which are perpendicular to the axes of symmetry and intersect each other at 120. Hexagonal prisms, hexagonal bipyramids, and rhombohedra are common forms.
FIG. 1. Body-centered cubic. Structure

of Cr,
Fe
(alpha), Li,
Na, K, Mo, Ta, V,
W.
Face-cenStructure of Ag, Al, Au, Ca, Ce, Co (cubic), Cu, Fe (gamma), Ir, Ni, Pb, Pt, Th, A.
FIG. 2. tered cubic.
FIG.
3.
Hexagonal
close- packed. Structure of Be, Cd, Ce, Co,
Hf, Mg, Os, Zn, Zr.
Ti,
Tl,
FIG.
type.
(grey).
4.
Diamond
FIG. 5.
Sodium chlo-
FIG.
6.
Cesium chlo-
Structure of
Si,
C
Sn
(diamond),
ride type. Structure of lithium, sodium and potassium halides: CaO,
ride type. Structure of
CsCl, CsBr, Csl, T1C1, TIBr, TIL
MgS, VN, NiO, CoO, FeO, AgCl, AgBr, PbS, MgO, CoF.
SiO,
546
APPENDIX
FIG.
type.
7.
Zinc oxide Structure of
FIG.
8.
Zinc sulfide
(sphalerite) type.
Structure of ZnS, HgS, CuCl, CuBr, Cul, Agl.
ide type.
ZnO, Agl, TaN, A1N,
Cuprous oxStructure of Cu 2 O, Ag 2 O.
FlG. 9.
BeO
FIG.
10.
Calcium
,
FIG. 11. Rutiletype.
FIG. 12.
Manganous
,
fluoride type. ture of CaF 2
StrucLi 2 S,
Structure of TiO 2
PbO 2
FeF 2 NiF 2
IrO 2
, , ,
MnF 2
ZnF 2 SnO 2
,
Li 2 0,
Cu 2 Se,
,
Na 2 S,
, ,
TeO CoF 2
2,
,
hydroxide type. Structure of Mn(OH) 2 ZrS 2f CdI 2 Mg(OH) 2 Ca,

,
BaF 2 ,PbF 2 ,SrF 2 ,HgF 2 ThO 2 CdF 2 Ce0 2

,
Nb0 2
UO
2,
PrO 2 SrCl 2
,
Ra-
tio of radius of radius of > 0.6.
MoO WO VO MnO Ra2,
MgF
(OH) 2
2,
2,
2.
to
tio of radius of radius of < 0.6.
to
FIG.
of
13.
ZnS, type.
Wurtzite, Structure
FIG. 14.
NiAs
type.
NH
4 F,
CdS, A1N.
MgTe,
BeO, ZnO, CdSe,
Structure of FeS, CoS, NiS, FeSe, CoSe, CoTe.
type.
FIG. IS. Perowskit Structure of

.
,
CaSnOs,
CaTiO 3 KIO 3 CaZrOs, LaAlO 3l

8.
KMgF
is
This system
ctess, crystals of
(4)
which
often divided so as to give a Rhombohedral may be referred to 3 axes, all equal and all
inclined unequally.
Crystals with three non-interchangeable at right angles to each other. The rhombic symmetry prism and rhombic pyramid are common forms.
Crthorhombic.
axes of
CRYSTAL FORMS
AND
TYPES
OF CRYSTAL LATTICE
547
Crystal with a single axis of symmetry but (5) Monoclinic. not three-, four-, or six-fold. Two additional axes of reference are chosen at right angles to the axis of symmetry and usually oblique to each other. A rhombic prism having a two-fold axis, a plane, and a center of symmetry is a common form. Crystal possesses no direction of symmetry. (6) Triclinic. Reference axes are non-interchangeable and in general at oblique angles. Two classes, with and without center of symmetry.
Appendix VI
QUALITATIVE ANALYSIS SCHEME
549
550
6
3
9
IJ
50
|u
50
O
I
o N
îcu
d
ac
ZnS,
.s
and
OF
BaCrO4
HCI
ecipitate:
s
pitate:
ANALYSI
in
lve
O
cj
5
a
..
!
5.
a a Sffi^d ~
8
|s-i%
Cu
<
PQ
- I aa *g oo ^z ^
1^
H
in
absen
prese
MnC>2.
produce
and
8
peroxide.
Dissolve
co
*i S s V w
(
s
TJ OT*
Precipitate
HNO
Phosphate Phosphate
Q< s
A. B.
Precipitate:
Add
bismuth
Violet
HMn0
552
553
"8
03
55
55 CJ
s&
^
C3
.2E
si
is
o
(/i
I
p
*3 J2
Z ^ S H g ^
&5
& > O U S
>,
3 I
Oj
-2 O
o o 4-> ^
J'l
03 -g
IT)
û
J
PQ
s 8 e ^ O
1^
554
CQ
So
s
c/
1 d
fe
1
1
I
"
o--
* S
o
.
g*"J
*
o
53
ffi
crJ
S
=Scrt
14
U
1
*
C3 "O
03
6
U s
181
CO
PQ
.s
s-
9
Q
CTJ
t?
111 >S^f2
555
Appendix VII
STRUCTURE OF MOLECULES
LINEAR
AND
, ,
IONS
,
HgCl2 (g), HgBr2 (g), Hgl,(g), CO2 C 3 O2 SCO, C4 H2 CH 3 CN, CH 3 NC, CS,, C2 N2 H2 CN2 N,~, NNO, CH 3 MgI, FHF-, BrIBr-, ClIBr-, AuCl2-, ~ I3 (with 3 electron pairs Ag(CN)-, BO2-, BeO2
, ,
,
about center
I?).
PLANE BC1 3) B(CH 3 ) 3 NOr, CO,, C(NH 2 ) 3 +, SO3) TRIANGULAR CuClr, Ni(CN)~, H 2 CO, OCC1 2 (C1-C-C1, 117), SCClj (C1-C-C1, 116), CH 3 NO2 (O-N-O, 127).
,
PLANAR
CH
9(
(HCOOH)
2 (g),
CH NNCH
3
3 (g).
BENT OR V-SHAPED
FOF(100 ),C1OC1(115 ),OC1O(125),C1O -(114 ) ONC1 (125), ONBr, C1SC1 (103), (CH 3) 2 O (111), O3) (CH 3) 2S, ONO (110-120), NO,- (132), OSO
!!
(122),
HS
2
(92),
H 0(105).
2
PYRAMIDAL
PF
(F-P-F, 104), PC1 3 (C1-P-C1, 101), PBr3 (Br-P-Br, 100), PI 3 (I-P-I, 98), AsF3 AsClj (Cl-As-Cl, 103), AsBr3 (Br-As-Br, 100), AsI 3 (I-As-I, 100), SbCl 3 (Cl-Sb-Cl, 104), SbBrs P(CH 3 ) 3 (Br-Sb-Br, 96), SbI 3 (I-Sb-I, 98) (C-P-C, 100), PFCli (C1-P-C1, 102), N(CH 3) 3 (C-N-C, 108), NH 3 (H-N-H, 108), SO 3 (O-S-O, 111), ClOr (O-C1-O, 107).
3
,
~
,
SQUARE PLANAR
TETRAHEDRAL
and molecules of Pd++, Pt++, Cu++ Ag+ + AU+++, Ni ++ (if diamagnetic), IC1 4~.
4
XY
,
ions
P4
As4,
,
SiQr 4
Ni(CO) 4 NH 4+ BFr, BeF-, Li(NH 3 ) 4 A104 -, S04 - 2 P04- s H 2 P02-, ClOr,

, , , ,
556
STRUCTURE OF MOLECULES
AND
IONS
, ,
557
MnO4-, MnO4~, SnBr4 Pb(C2H 6) 4 TiCl4 and other Cu+ complex GeCU, SiCl 4 Cu(CN) 4 ++ and other ions, Ni(H 2 O) 4++, Ni(N 2 H 4 ) 2 paramagnetic complex ions of Ni++, (CH 3 ) 3 PtCl, and Pt+ 4 when is Zn, Cd, or Hg, complex ions, M(CM) 4 SnS4 ~ 4 AsS 4~ 3 CC1 4 and all carbon compounds with four single bonds, H 2 Fe(CO) 4
CrO 4
,
, ,
M
8
TRIGONAL
BIPYRAMID
PC1 5
PF PF
5,
C1 2
MoCl e (CH 3) SbX2

,
SQUARE
PYRAMID
OCTA-
IF 6
HEDRAL
In general, all 6 compounds and complex ions. MoF 6 (as gases) the M-F distances In UF 6 6 of the three axes are different. In MoS 2 (crystal) six sulfur atoms form a triangular prism about a
,
WF
XY
molybdenum atom.
SEVEN-
ZrF 6
IF7
(?).
CORNERED POLYHEDRON
HEXADRAL
(CUBE) OR SQUARE ARCHIMEDEAN
W(CN)
-4
8
,
Mo(CN) 8
-4
,
and Ca(C 2 H 6OH) 8++ prob

(?),
4 ably the former. (ZrF8)~
(TaF8)~ 3
(?).
ANTIPRISM
Appendix VIII
DENSITY OF
WATER
DENSITY OF WATER IN GRAMS PER CUBIC CENTIMETER
WHEN WEIGHED
APPARENT DENSITY OF WATER, IN AIR WITH BRASS WEIGHTS, IN GRAMS PER CUBIC CENTIMETER
558
Appendix IX
DENSITY OF MERCURY
DENSITY OF MERCURY IN GRAMS PER CUBIC CENTIMETER
559
Appendix
EQUILIBRIUM PRESSURE OF WATER
WATER VAPOR
PRESSURE IN MM. OF MERCURY
(Cf. also Fig. 2,
Chap.HI)
60
Appendix XI
SOLUBILITY PRODUCTS
Bromides
AND
ACID
IONIZATION CONSTANTS
K
X 10-* 6.3 X 105.2 X 10~ 23 3.3 X 10" 13 3.6 X 105.3
CuBr PbBr 2
Fluorides
Hg 2 Br 2
AgBr
TIBr
Carbonates
BaF 2 CaF 2
1.7
MgF
PbF 2
SrF 2
3.4 6.4
2.7
X X X X X
10-*
10-"
10- 8 1010-
BaCO, CdCOa CaCOs CoCOs CuCOs FeCOs
PbCO 8
MgCOs-3H 2O
MnCOs Hg 2C0
NiCOs Ag 2 CO, SrCOs ZnCOa

Chlorides
CuCl
PbQ
Hg
2
Cl 2
AgCl
T1C1 BiOCl(BiO+,
Chromates
BaCrO 4 PbCrO 4 Ag 2CrO 4

SrCrO 4
561
562
APPENDIX
XI
SOLUBILITY PRODUCTS
563
Appendix XII
BUFFER SOLUTIONS
The following solutions may be employed to maintain desired mcentrations of + or OH~. These concentrations are expressed pH = logic 1/(H+) e.g., 0.01 JV H+ has a pH of 2.
SORENSEN'S PHOSPHATE SOLUTIONS
KH PO
2
4,
9.078
g.
per
liter,
and Na 2 HPO 4 -2H 2 O, 11.876
g.
per
liter
ACETIC ACID-ACETATE SOLUTIONS, BY WALPOLE-CLARK
CLARK AND
L,UBS,
BORATE SOLUTIONS
564
Appendix XIII
INDICATORS
CLARK AND LUBS'
Abbreviations:
v, violet.
LIST,
COVERING RANGE FROM STRONG ACID TO STRONG BASE

red; y, yellow; b, blue; pu, purple; o, orange;
c, colorless; r,
INDICATORS IN
COMMON USE
565
Appendix
XIV
CHANGE OF
RESISTANCE OF METALS
WITH TEMPERATURE
R/Ro is the ratio of the resistance to the value at conductivity of mercury.
C. Insert shows supra-
0.26
230
180
130
80' C
566
Appendix
XV
HEAT OF METALS AND COMPOUNDS AT LOW TEMPERATURES

SPECIFIC
1.1
1.3
1.5
1,7
1.9
2.1
2.9
2.5
2.7
logT
567
Appendix
XVI
COVALENT BOND ENERGIES AND ATOMIC

RADII
Values from Pauling. Nature of Chemical Bond. Cornell University Press, 1939
COVALENT BOND ENERGIES
568
COVALENT BOND ENERGIES AND ATOMIC

TETRAHEDRAL COVALENT RADII
RADII
569
OCTAHEDRAL RADII
Appendix XVII
TABLE OF CONVERSION FACTORS

Values in agreement with International Critical Tables
Length and volume

1 1 1
Meter = 39.37 in. = (100/2.54) Yard (U.S.) - 91.44018 cm. Yard (British) - 91.43992 cm.
Liter
in.
1 1
1
1
1 1
1000.027 cm. 3 = 28317.0 cm. 8 Gallon (U.S.) - 3785.4 cm. Gallon (British) - 4546.1 cm. 8
log log log log
Cubic foot (U.S.)
Quart, dry (U.S.) - 1101-23 cm. 8 Quart, liquid (U.S.) = 946.358 cm. Fluid ounce (U.S.) - 29.5737 cm. 8
8
log log
log log
'
log
log
1.9611371 1.9611350 3.0000117 4.4520474 3.5781157 3.6576376 3.0418770 2.9760557 1.4709057
Weight 1 Grain
1 1 1
64.799 mg.
g.
Ton, short (2000 pounds) = 907.185 kg. Ton, long (2240 pounds) == 1016.047 kg.
28.350 g. Ounce (avoirdupois) Pound (avoirdupois) - 453.59243
1000/2.2046223
log log log log
'
<
1.8115677 1.4525458 2.6566658 2.9576958 3.0069138
~ in. (U.S.) = 68947.3 dynes cm. 2 Centimeter of water at 4 C. = 980.638 dynes cm." 2 2490.827 dynes cm." 2 C. (U.S.) 1 Inch of water at 4 2 1 Centimeter of mercury at 0C. = 13332.24 dynes cm." 1 Inch of mercury at C. (U.S.) = 33863.95 dynes crn.~ 2 Density = 0.999973 1 Gram per milliliter = specific gravity, t/4 8 g. cm.~ 8 1 Pound per cu. in. (U.S.) - 27.67974 g. cm.1 Pound per cu. ft. (U.S.) 0.016018 g. cm.-* 3 1 Pound per gal. (U.S.) - 0.1198257 g. cmr
1
Pressure
1
Pound weight per sq.
log log log
<
log log
4.8385173 2.9915090 3.3963436 4.1249031 4.5297377
log log log

log
>
1.9999883 1.4221621 2.2046183 T.0785502
Energy 1 Cubic centimeter-atmosphere 0.10133

(absolute)
1
0.101325 joules
log log log log log
'
Gram
t
1
(15) British Thermal Unit British Thermal Unit British Thermal Unit
calorie
4.185 joules absolute (39 F.) - 1060.4 joules (abs.) 1054.8 joules (abs.) (mean) (60 F.) = 1054.6 joules (abs.)
<
T.0057167 0.6216955 3.0254697 3.0231701 3.0230878
570
TABLE OF CONVERSION FACTORS

Work i Watt
1
1 1 1 i
571
(International) - 1.00032 watt (absolute) 9.80665 watt (abs.) Kilogram-meter per sec. Foot-pound per sec. (U.S.) = 1.355821 watt (abs.) Horsepower (U.S., British) - 746.00 watt (abs.) Horsepower (Continental Europe) - 736.00 watt (abs.) Cheval-vapeur (75 kg.-m. per sec.) - 735.499 watt (abs.)
log log log log log log
* -
0.0001390 0.9915207 0.1322022 2.8727388 2.8660778 2.8665820
Temperature Fahrenheit * F. Reaumur x R.
32) (5/9) (* (5/4) x C.
Appendix XVIII
THE ELECTRON STRUCTURE OF THE ELEMENTS
572
THE ELECTRON STRUCTURES OF THE ELEMENTS
573
574
APPENDIX
XVIII
Appendix
XIX
ABUNDANCE OF THE ELEMENTS

L ABUNDANCE
IN
THE SUN, (ATOMS PER 10,000 ATOMS OF

(Values
Si)
by H. Brown)
575
576
APPENDIX XIX
IL ABUNDANCES OF ELEMENTS IN METEORITES (PER CENT BY WEIGHT)

(Values by H. Brown)
Appendix
XX
TABLE OF DENSITIES, MELTING POINTS, BOILING

POINTS,
COLORS,
AND
SOLUBILITIES
OF INORGANIC COMPOUNDS
Values for densities are in grams per cc. Temperatures 15-25 C. Values for solubilities are in grams of anhydrous salt per 100 grams of water solution. Abbreviations for colors: bk, black; bl, blue; br, brown; c, colorless or white
if finely divided; d, dark; gr, green; gy, grey; 1, light; or, orange; pk, pink; pu, purple; r, red; ro, rose; sil, silver; v, violet; w, white; y, yellow
577
578
APPENDIX XX
TABLE OF INORGANIC COMPOUNDS
579
580
APPENDIX XX
581
582
APPENDIX XX
583
584
APPENDIX XX
585
586
APPENDIX XX
587
588
APPENDIX XX
589
590
APPENDIX XX
TABLE OF INOROANIC COMPOUNDS
591
59i
APPENDIX XX
593
594
APPENDIX XX
TABLE OF INORGANIC
COMPOUNDS
595
596
APPENDIX XX
597
598
APPENDIX XX
599
Index
Acetamide, 194
Acetate, buffer solutions Acetic acid, 194
of,
564
Aluminon test, 99 Aluminum,

acetate, 98
alloys, 92
>
Acetylene,
properties, 291
290 Acetylides, 292

series,
analytical properties, 98 boride, 82 carbide, 291
Acids,
def.,
513
organic, def., 293

resins, 302 Actinide elements,
carbonate, 94 halides, 95 hydroxide, 93

isotopes, 506 nitride, 93
Aery late
electron structure, 462

ionic radii,
464
oxidation states, 463
occurrence, 90 oxidation potential, 81, 93 oxide, 93
Actinium,
occurrence, 465
isotopes,
series, 487,
preparation of metal, 90 properties of metal, 81, 93

solder,
sulfate,
466 488
345 96
Adsorption, coefficient, 513 Agate, 314 Air, 13, 19, 23 Alabandite, 387
Alcohol,
def.,
sulfide, 94,
98
Alundum, 94
Amalgam^.
alkali,
43
293
ethyl, production,
306
Aldehyde,
Alkali,
def.,
293
195 radium, 62 Amatol, 197, 300 Amber, 302 Amblygonite, 42
ammonium,
bicarbonates, 49 halides, heat of formation, 40 metal elements, 36 nitrates, 53

silicates,
Americium,
isotopes,
480
chemistry, 480 Amide, 194
317
Alkaline earths, 57
Alpha-particle, 14, Aliphatic compounds, 289 Allotropy, def., 513
492
Amidosulfonic acid, 194, 265 Amido-acids, 194 Amino-acids, 298
Ammonia,
Almandite, 320 Alum, def., 97 Aluminates, 95
manufacture, 189
properties of, 191 reactions of, 193, 213
601
602
Ammoniates, 193
INDEX
pentoxide, 236
potentials, 242
Ammonium,
amalgam, 195
analytical, 198
preparation, 220 reactions of, 224

sulfides,
bromide, 196 carbamate, 197

carbonate, 197 chloride, 196 cyanate, 298 dichromate, 377 dithiocarbamate, 198 hydrolysis of ion, 196 hydroxide, 194
electron structure, 189 hypoiodite, 202
238
235
tetroxide, 235
trioxide,
Antimonyl compounds, 237

Apatite, 60, 217
Aqua
regia,
214
cobaltichloride, 427
Aquapentimmine
Aragonite, 68 Argentite, 113
Argon,
isotopes,
506
molybdate, 380 nitrate, 196, 215

oxide, 195
persulfate, 198 phosphate, 197, 231
occurrence, 13 origin, 14
physical properties, 14 uses, 17, 18

Arizonite, 322
phosphomolybdate, 380
polysulfide, 197
sulfate, 197
sulfide, 197,
Aromatic compounds, 290

Arsenates, 235 Arsenic acid, 235
Arsenic,
analytical properties, 240
250
thiodyanate, 198 vanadate, 363 \mpere, def., 513
Amphibole group, 319

Analcite, 319
Anatase, 336 Andalusite, 320 Andradite, 320 Anglesite, 342
halogen compounds, 237 in shot, 222 isotopes, 507 modifications of, 219 occurrence, 217 potentials, 242 preparation, 220 reactions of, 224 513
separation from selenium, 267 sulfides, 238 trichloride, 235
trioxide,
Angstrom
unit, def., 513

def.,
Angular momentum, Anhydride, def., 513

Anhydrite, 72 Aniline, 299
234
Anode, def., 513, 525 Anthophyllite, 319

Anthracene, 290 Antimonates, 227 Antimonides, 240
Antimonites, 236
white, 234 Arsenides, 240
Antimony,
alloys,
222
analytical properties, 240 butter of, 238
Arsenious acid, 234 Arsine, 224 Asbestos, 322 Aspirin, 307 Astatine, 156, 183 isotopes, 511 Atacamite, 102 Atmosphere, def., 513 Atom, def., 513
halogen compounds, 237 isotopes, 508 modifications of, 219 occurrence, 217
Atomic,
bomb, 499
"clock", 192
number,
def.,
513
INDEX
weight, def., 514 weights, light elements, 485 weights, tables, back inside cover Augite, 319 Aurate ion, 125
Austenite, 405 Autunite, 370 Avogadro's,
rule,
6Q3
Berkelium, 482 Berlinate, 417 Beryl, 60, 319 structure, 323 Beryllate, 66 Beryllia, 63
Beryllium, alloys, 62
analytical, 77
number, 514 514
borohydride, 88
carbide, 288
Azides, 200 Azurite, 102, 112
Babbitt, 345
carbonate, 67 halides, 69 hydroxide, 65

isotopes, 506 oxide, 63 properties of metaf, 58, 60 sulfate, 71
Baddeleyite, 333
Bakelite, 303 Bar, def., 514 Barbital, 308 Barites, 60, 73
Bessemer process, 408

Bua-particle, 486 Beta-radiation, 485 Bicarbonate, equilibrium bonate, 285
Biotite,
Barium,
carbonate, 69
ferrate,
with car-
417
halides, 71
319
hydroxide, 67 isotopes, 509 nickelite, 431 nitrate, 76 occurrence, 60 oxide, 63

perferrite,
Bismite, 218
Bismuth,
alloys, 223
analytical properties, 241 basic compounds, 236
417 peroxide, 65 source of oxygen, 24
properties of metal, 58, 59, 60 selena te, 260 spectra, 79

sulfate, 73,
259
analytical, 267
thiocarbonate, 265 Baryta, 63 Basalt, 321

Base, 514 Base element, 514 Bases, relation to ionic sizes, 26 Basic acetate, separation, 419
Battery, def., 525 Bauxite, 88, 92 Bayerite, 92 Bell metal, 106 Benitoite, 319, 323 Benzedrine, 307
Benzene, 290
halogen compounds, 237 hydroxide, 236 isotopes, 511 monoxide, 236 occurrence, 218 pentoxide, 237 potentials, 242 preparation, 220 properties, 221 radioactive properties, 443 suifide, 238 Bismuthates, 237 Bismuthides, 240 Bismuthine, 224 Blast furnace, 404 gas, 270 Blasting gelatine, 299 Bleaching, 161, 177, 283 Bleaching powder, 177 Blue prints, 417 Body-centered cubic crystals, 545 Bohmite, 94 Bohnalite, 61
.
604
Bohr atom,
2
INDEX
Buffer solutions, table of, 564 Butadiene, 304
Boiler scale, 72
Boiling point, def., 514 Boiling points, tables of, 577 Bonds, non-polar, 271, 568
Cacodyl, 227
Cadmium,
Boranes,
properties, 87 reactions, 88
complex
ions, 134 halides, 136
Borates, 83 buffer solutions of, 564
isotopes, 508
Borax, 84
Borazole, 89 Bordeaux mixture, 111 Boric acid, 83, 89
Borides, 86 Bornite, 102
metallurgy, 131 oxides, 135

properties of metals, 130, 133
sulfate, 136
sulfide, 137
Boron,
analytical,
halides,
89 86 hydrides, 87 isotopes, 506
Calamine, 131, 319 Calcite, 68 Calcium, aluminate, 95, 327

analytical properties, 77 bicarbonate, 69 carbide, 76, 289 carbonate, 68 structure, 273
occurrence, 81
oxides, 83
phosphate, 85 preparation, 82
properties, 82, 83 Borosilicates, 320
Boryl sulfate, 85 Brass, 106 Braunite, 386
columbate, 358 cyanamide, 76, 191, 298 cyanide, 298 fluoride, type of crystal lattice, 544 halides, 69
hydride, 76 hydroxide, 66
isotopes, 506 nitrate, 76
Breeding factor, 502 Brevium, 470 Britannia metal, 345 British thermal unit, Bromate, 181
oxide, 63, 65
def.,
514
phosphate, 77, 231

polysulfide, 263 properties, 58, 59,
Bromic
acid, 174, 181

ion, 173
60
Bromide, Bromine,
312 spectra, 79
silicide,
analytical properties, 183 fluoride, 167 hydrate, 163

hydrolysis, 166
isotopes, 503 occurrence, 159 oxidation potentials, 164, 174 physical properties, 159 potentials, 185
sulfate, 72
sulfide,
77
titanate,
332
Californium, 482 Calomel, 142

Calorie, def., 514
Carbides, 288
preparation, 160
properties, 82, 83
Carbohydrate, 293 Carbon, amorphous, 275
compounds, structure, 271

cycle, 285 dioxide, 282
Bronze, 106
Brown
ore,
401
Bucher process, 297
properties, 283, 292
INDEX
disulfide,
605
compounds, 455-461
fluoride,
289 hydrogen compounds, 289 monofluoride, 276 monosulfide, 289

monoxide,
analysis, 277 equilibrium in blast furnace, 404 in fuels, 281
457
occurrence, 454
properties, 453
properties, 278
nitride, 295
occurrence, 273
oxysulfide, 289
properties, 277
suboxide, 277
tetrachloride, 294
Carbonates, analysis, 286 equilibrium with bicarbonate, 285 hydrolysis, 286 structure, 273 Carbonic acid, 285 Carbonous acid, 277, 282 Carbonyl chloride, 279 Carbonyls, preparation, 278 Carnalhte, 51, 60, 159 Carnotite, 357, 370 Caro's acid, 264 Cassiterite, 341 Castncr process, 45 Catalyst, def. of, 514
subgroup, 452 Cerussite, 341 Cesium, analytical, 55 chemical properties, 38, 42 chloride, type of crystal lattice, 545 hydroxide, 44 isotopes, 509 occurrence, 41 oxides, 44 physical properties, 37 preparation, 42 spectra, 38 Chabazite, 319 Chalcocite, 102 Chdlcopyrite, 102 Charcoal, 275 Chemiluminescence, 514 Chile saltpetre, 53 Chloramine, 201 Chlorate, 179 Chloraurate ion, structure, 101 Chlorazide, 201 Chloric acid, 179
Chloride,
complex
ions, 172
Cathode, def., 514

rays, def., Celestite, 73
Cell,
of lime, 177 properties of ion, 172
514
Chlorine,
analytical, 183 dioxide, 178
dry, 392
electric, def.,
hydrate, 163
525
lead,
354
hydrolysis, 165, 176 isotopes, 506
Cellophane, 302 Celluloid, 302

Cellulose, 293, 300
monoxide, 176
occurrence, 159 oxidation potentials, 164, 169 oxides, 176, 178 physical properties, 159 potentials, 185 preparation, 160 reactions of, 164 reaction with carbon monoxide, 279
Chlorite, 175, 319
acetate, 301
forms, 301 industry, 300

trinitrate,
299
Cement,
Portland, 327 magnesium, 70 Cementite, 406
Centigrade temperature, 514 Cerium, analytical. 457
Chloroform, 294 Chloromine, 201
Chloropentamine cobaltichloride, 432 Chloroplatinic acid, 425
606
Chloroplatinous acid, 446 Chlorosulfuric acid, 266
Chlorpicrin, 293
INDEX
Cobaltic,
Chromate, compounds, 377 Chrome, alum, 376

green, 375
complex ions, 426 compounds, 426 coordination compounds, 428 Cobalticyanide, 426
Cobaitite, 420, 429
orange, 377 steel, 371

yellow, 377 Chromic, acid, 377 complex ions, 376 compounds, 374 Chromite, 370 compounds, 374
Cobaltocyanide ion, 426 Cobaltous compounds, 425 Colemanite, 82 Collodion, 302 Colloid, def., 514
Colors, of inorganic
compounds, 577
Columbite, 358
Columbium (see Niobium) Complex compounds, nomenclature,

428
Chromium,
analytical, 384
Component, 514
Concentration, 515 Concrete, 324 Conductance, 515 Constantan, 106, 423 Contact process, 254
metallurgy, 370
isotopes, 506
occurrence, 370 oxidation potentials, 374, 385

Chromous compounds, 374

Chromyl, 378
Chrysocolla, 102, 319 Cinnabar, 139
Conversion factors, tables, 570 Coordination number, 101, 515 Copper,

alloys, 106
analytical, 112 arsenide, 242

isotopes, 507
Claude,
liquefaction process, 24 nitrogen process, 190
Claude tite, 218 Clay, 322 Cleaning solution, 376 Clinochlore, 319
Coal, 273
-tar,
metallurgy, 102 occurrence, 102 oxidation potentials, 107, 128 properties of metal, 103, 106 Cordite, 299 Corrosive sublimate, 144
ammonia from, 189
Cobalt, aluminate, 98
analytical, 431
Corundum, 90 Cosmic Rays, 503 Coulomb, 515

Covalent bond, 515 energies, 568 radii, 569 Cristobalite, 315 Critical mass, 499
Critical pressure, 515 Critical temperature, 515
426 compounds, 425 green, 426

blue,
isotopes, 507
metallurgy, 421 occurrence, 420 oxidation potentials, 424

potentials,
Critical
volume, 515
Cryolite, 90, 159
450
Crystal,
classes,
physical properties, 422

reactions, 424 sesquioxide, 426
544
cubic, 544 lattice, types, 544
yellow, 427
Cupferron, 419
INDEX
Cupric,
60?
ammonia
ion, 101,
110
Diatomaceous earth, 314 Diazonium chloride, 209

Dichromate,
ferrocyanide, 112
halides, 110
hydroxide, 110 ion, 109 nitrate, 111 oxide, 110 phosphate, 112 sulfate, 111 sulfide, 109 Cuprite, 102
determination of iron, 419 acid, 376 Dielectric constant, 515 Diffusion law, 515 Dimagnetic, 515 Dimethyl glyoxime, test for nickel, 431
Dichromic
Diopside, 319
Diorite, 320
Cuprous,
compounds, 108
cyanide, 108 oxide type of crystal lattice, 544 Curie, dcf., 492, 516
Diphenylamine, 216
Disaccharide, 293 Disiloxan, 314 Distribution law, 516 Dithionic acid, structure, 261
Curium,
isotopes, 481 chemistry, 481 Cyanamide, 298 Cyanates, 297
Dolomite, 60
Drierite, 73
Dry
cell,
392
Duralumin, 92
Duriron, 312 Dyes, 306 Dynamite, 297
Cyanide,
297 preparation, 295 Cyanite, 320 Cyanogen, 295 chloride, 295 Cyanogenamide, 298 Cyclonite, 299 Cyclotron, 492
complex
ions,
Dyne, 516 Dysprosium,

analytical, 457
compounds, 455461 occurrence, 454 physical properties, 453

Edison
cell,
Dacite, 320 Dakin's solution, 177 Davy, 160 308 Deacon process, 165 Dechenite, 357 Decomposition voltage, 515 Degree of freedom, 515 Deliquescent, 515 Densities, tables, 559, 577 Density, 515 conversion factors, 570 Deuterium,
431
Effluent, def., 516

Electrolysis, mechanism, 525 Electrolytes, ionization, 541
DDT,
Electromotive force, 516 Electron, 1, 516 affinity, 516

in
ammonia, 192
487
pairs, creation,
structure of elements, 572 Electropositive element, 516
Elements, def., 516

in meteorites, in sun, 575
occurrence, 1 physical properties, 11
576
Devarda's
alloy,
216
Eluate, def., 516
Diamond,
physical properties, 275 type of crystal lattice, 544 Diaspore, 94
Emery, 94
Enantio tropic, 516 Energy, 516
conversion factors, 570
608
Enstatite, 319
INDEX
complex cyanides, 413, 415 compounds, 411 reaction with permanganate, 397
Fire extinguisher, 97 Fischer-Tropsch, process, 305
Fission,
activity, 499 nuclear, 496
Entropy,
def.,
516
Epidote, 319
Epsom
salt,
71
Equilibrium, 516 constant, 517 Equivalent, 516
Erbium,
analytical, 457
compounds, 455-461 occurrence, 454 physical properties, 453

Erg,
def.,
products, 497 Fixation of nitrogen,
ammonia
process, 190
cyanamide
process, 191
517
nitric oxide process,
211
Erythrite, 420 Ester, 293 Ether, 293 Ethyl, borate, 85 chloride, 294
gasoline, 305 radical, 293
Flint glass, 326 Flotation, 103
Flue gas, 405 Fluocarbons, 295
Fluoplumbic
acid, 353
Ethylene chloride, 294 Europium, analytical, 457 compounds, 455-461 occurrence, 454 physical properties, 453
Eutetic, def., 517
Fluorescence, 465 Fluoride, complex ions, 172 ion, 171

Fluorine, as oxidizing agent, 165
isotopes,
506
Explosive, 299
occurrence, 159 oxidation potentials, 164, 185 oxides, 176 physical properties, 159 preparation, 160
reactions, 164-166 Fluorite, 69
Face-centered cubic crystals, 545 Fahrenheit temperature, 517 Farad, def., 517
Fluorspar, 60, 69, 159

Fluosilicic acid, 313
Faraday, def., 517 laws, 525

Fehling's solution, 108 Feldspar, 319 weathering, 322 Feldspathoid, group, 319 Fergusonite, 454 Ferrates, 417
Ferric,
Flux, 517 Fools' gold, 412
Force, def., 517
Formal
charge, 26, 158, 517 concentration, 517
potential, 517
complex cyanides, 415 compounds, 413

401 Ferromanganese, 387
Ferrites,
Formaldehyde, 292 Formic acid, 277, 282, 292 Forsterite, 319 Francium, 56
isotopes, 511 Franklinite, 131 Frary metal, 345
Ferrosilicon, preparation,
312
Ferrotungsten, 372
Ferrovanadium, 358
Ferrous, chromite, 370
Frasch process, 247 Free energy, def., 536

relation to electromotive force, 537
INDEX
values and their use, 537 Freon, 294 Fructose, 293 Fugersonite, 358
Glucose, 293 Glyptal, 303 Gold,
analytical, 126
609
complex cyanides, 123, 125

Gabbro, 321 Gadolinite, 454 Gadolinium, analytical, 457 compounds, 455-461 occurrence, 454 physical properties, 453 Galena, 342
Gallium,
analytical, 151
fulminate, 126 halides, 126

isotopes, 510
metallurgy, 123 occurrence, 122 oxidation potentials, 125, 128 oxides, 125 properties of metal, 103, 124 sulfides, 126
Goldschmidt reaction,
93,
370
compounds, 150
isotopes, 507
Gram, 518
atom, 518
molecule, 518 Granite, 320 Graphite,
blue, 276
metal, 150 occurrence, 148 potentials, 155
Gamma-rays, 487
Garnet, 90 group, 320
Garnierite, 420
moderator, 501
physical properties, 274, reactions, 276 structure, 276
276
Gas, 517 constant, 517 natural, 273 Gasoline, 305

Geiger-Nuttall, relation, 491 Gelatine, blasting, 299
Graphitic oxide, 276 Gravitation constant, 518

Grossularite, 320
Guncotton, 299 Gunmetal, 106
German
silver, 106,
423
Germanium,
analytical, 356
Gunpowder, 215 Gypsum, 60, 72
compounds, 346
isotopes, 507
Haber
process, 190
occurrence, 341
Hafnium, compounds, 339

isotopes, 510
occurrence, 332
properties, 334 Half reactions, 525, 534 Hall process, 90
separation from selenium, 268 tetrabromide, 268 Gibbsite, 94

Glass, 325
Halogen,
halides, 166 nitrides, 201
coloring of, 326
composition, 326
decolorizing of, 392
devitrification of,
327
manufacture, 326 ruby, 248 types, 248 Glauber's salt, 53 Glossary, 513 Glucinum, 57
occurrence, 159 oxidation potentials, 164, oxy-acids, 174 reactions, 164, 293
69
Hanford, reaction, 500
Hard
water, 74 Hauerite, 386
Hausmannite, 386
610
Heat,
def., of
INDEX
ion, 7
518
isotopes, 506
of ionization of water, 30 of neutralization, 30
Helium/*
isotopes,
506
occurrence, 4 oxidation-reduction couple, 8 peroxide, oxidation potentials, 34

preparation, 30 properties, 31
structure, 30
use, 32 physical properties, 6
occurrence, 13 mass three, 16

uses, 17
Hematite, 401 Heulandite, 319 Hexagonal,

close-packed crystals, 545 crystal system, 546
polysulfide, structure, 261 preparation, 9, 269, 312
reactions, 6
reaction with halogens, 165

selenide,
Holmium,
analytical, 457
compounds, 455, 461 occurrence, 454

physical properties, 453 Hopcalite, 279
physical properties, 249 reactions, 251

sulfide,

reactions, 249
telluride,
Hornblende, 319
Hornsilver, 113

reactions, 249 Hydrogenite, 312 Hydroiodic acid, properties, 181 Hydrolysis, def., 518 Hydrous oxide, 518 Hydroxylamine, 199 disulfonate, 202 disulfonic acid, 195 electron structure, 189 Hypersthene, 319 "Hypo", 262 Hypobromites, 180
Humidity, 518 Hydrazine, 198

Hydrazoic acid, 200

Hydrides, 7
acid, properties, 169 Hydrocarbons, 289, 292 Hydrochloric acid, properties, 169 Hydrocyanic acid, 298 Hydrofluoric acid, properties of, 169 Hydrogen, atomic structure, 1 atomic torch, 10 bromide, 169
Hydrobromic
Hypobromous
Hypochlorous
acid, 181 acid, 165, 176
Hypoiodites, 180
chloride,
hydrates, 170 preparation, 167

properties, 169 commercial use, 10
Hypoiodous acid, 181 Hyponitrous acid,

preparation, 204
structure, 203
cyanimide, properties, 295

fluoride,
Hypophosphoric acid, 230 Hypophosphorous acid, 229

Hyposulfite, 262
action
upon
glass, 171
Hyposulfurous acid,
preparation, 167
properties, 169 halides, 167
iodide,
preparation, 261
Igneous rocks, 318

Illinium (see
Iliium,
preparation, 167 properties of, 169
Promethium)
423
INDEX
Ilmenite, 332
analytical, 449
Imide, 194 Imidosulfonic acid, 195 Indicators, 565
compounds, 443
isotopes, 510
Indium,
analytical, 152

Iron,
compounds, 152
isotopes, 508
metal, 149 occurrence, 148

potentials, 155 Inert gases, 14
analytical, 419
carbonyl, 418 grey cast, 404

isotopes, 507
Ink, 412
Inorganic compounds, table of properties, 578

Invar, 423 lodate, 181 lodic acid, 181
Iodide,
ion, 173 oxidation
metallurgy, 402 modifications, 401 occurrence, 401 oxidation potentials, 411, 450 physical properties, 402
pyrites, 243, 412 reactions, 411
by nitrous
acid,
208
oxidation, 164 Iodine,

analytical properties, 183 bromide, 167
chloride, 167
fluoride, 167
410 white cast, 404 wrought, 405 Isobar, def., 518 Isomerism, 518 Isometric, 543 Isomorphous, 518 Isotopes, def., 518
rusting,
hydrolysis, 165 isotopes, 509
Jadeite, 319

oxides, 174
Jargon, 339
pentoxide, 181 physical properties, 159, 169 preparation, 162

reactions, 164
Jena glass, 326 Jones reductor, 420 Joule, 518
Joule-Thomson,
effect, def.,
518
reaction with arsenious acid, 235 reaction with thiosulfate, 183 tetroxide, 182 tincture, 162
Kainite, 51 Kaolin, 323 Kaolinite, 319, 324 Keenes cement, 73
lodoform, 162, 294

Ion,
def.,
Kelvin scale, 518 Kennametal, 288 Kernel, atomic, 518

Kernite, 82
518
to acids and
structure, 556 Ionic radii, relation
Ketone, 293
Kidney
ore,
401
bases, 27 lonization,
Kieselguhr, 314
Kieserite, 71 Kilo, def., 518
constant, theory, 27 constants, 561

potential, 518
Krypton,
isotopes, 507
strong electrolytes, 541 Iridium,
612
Kurrols
salt,
INDEX
233
light,
65
stone, 68
Lactose, 293 Lake, 97
Limonite, 401
def.,
Lanthanide,
518
Lanthanum,
analytical, 457
Linde liquefaction process, 24 Linnolite, 420 Lipowitz metal, 223 Liter, def., 519
Litharge, 351
compounds, 455-461 occurrence, 454

physical properties, 453 Latent heat, 519 Lattice energy, 519 Lawrence, E. O., 492 Lazurite, 319 Lead, acetate, 353 alloys, 345 analytical, 355 arsenate, 235 azide, 201 carbonates, 354 chamber process, 256 chromate, 353, 377
dioxide, 351
halides, 352
Lithium,
alloys,
43
analytical, 55 atomic structure, 36
borohydride, 88 carbonate, 49 chemical properties, 38, 42 chlorate, 179

chloride, 51
fluoride,
49
hydroxide, 45
ionization potential, 37 isotopes, 506
nitride, 194 occurrence, 41 oxidation potential, 37
oxides, 44
hydroxide, 351
isotopes, 510
physical properties, 37 preparation, 42

spectra, 38
metallurgy, 344 monoxide, 351

nitrate,
353
occurrence, 351 oxidation potentials, 351

pencils,
42 Lithopone, 74, 137 Litmus, 565

'use,
276
Lodes tone, 413 Loschmidt's number, 519

Lucite, 302
phosphate, 355 properties of, 342

radioactive properties, 510 reactions of metal, 346
red, 351
silicate,
Lunar
caustic, 118
Lutecium,
analytical, 457
compounds, 451-461
355
occurrence, 454 physical properties, 453 radioactivity, 457, 490
storage battery, 355 sugar of, 353

sulfate,
sulfide,
353 354
Magnalium, 92
Magnesia, 63 alba, 67 Magnesite, 60, 68
tetraethyl, 305
white, 354
Le Blanc process, 46 Leclanche cell, 393 Lepidolite, 42, 319 Leucite, 319 Lewis, G. N., 543 Lime, 63 kiln, 64
Magnesium,
alloys, 62, 92
ammonium
69
phosphate, 77, 240
analytical, 77
carbonate, 68
chloride,
INDEX
process, halides, 69
61 3
law, 519
Dow
69
Mass
Masurium, 386
Matches, 221 Mega, def., 519
Melcanite, 102
Mellitic acid, 275
hydroxide, 66
isotopes, 506
metallurgy, 61 nitride, 61 oxide, 62
preparation of metal, 60 pioperties of metal, 58, 60 spectra, 79 sulfate, 72 uses, 61
Melmac, 303 Melting point,

Mercuric,
def.,
519
145
ammonia compounds,
chloride, 144
complex
iodide, 145
Magnetite, 401, 413 Malachite, 102, 112 Malonic acid, 277
Manganate, compounds, 393 ion, 389 Manganese, analytical, 396

bronze, 388 carbide, 387
cyanide, 146 fluoride, 145 fulminate, 146 iodide, 145 nitrate, 146 oxide, 144 sulfate, 146 sulfide, 146 thiocyanate, 147
compounds, 389
dioxide, 392 isotopes, 507
Mercurous, bromate, 143

carbonate, 143 chromate, 143 halides, 142, 143 ion structure, 142 nitrate, 143 oxide, 142 sulfate, 143 sulnde, 143

steel,
387
tetrachloride, 392
Mercury,
analytical, 147
isotopes, 510
Manganic compounds, 390 Manganin, 106, 388, 423

Manganite, 386, 392
Manganous,
carbonate, 391 complex cyanides, 391 ferrocyanide, 391 halides, 391 hyroxide, 391
metallurgy, 139 occurrence, 139 oxidation potentials, 141 properties of metal, 139 table of densities, 559
type of crystal lattice, 544 manganites, 392 oxidation of ion, 389 oxide, 391 sulfate, 391 sulnde, 391 Marcasite, 412 Marsh gas, 290 Marsh test, 241 Martensite, 407 Mass, def., 519
Meson, 503 Mesothorium, 488 1,488

Metals,
def.,
521
resistance at low temperature, 566

specific heat of, 567
rocks, 318 Metaphosphoric acids, 232
Metamorphic
Methacrylate, 302
Methane,
occurrence, 273
properties, 290
614
Methyl,
alcohol, 292
INDEX
Mosaic gold, 350 Mordant, 97, 349
Mortar, 66 Muriatic acid, 160 Muscovite, 319
borate, 85
orange, 565 violet range, 565
Mho,
def.,
519
Mustard
gas, 161
Mica, 322 Micro, def., 519 Microcline, 319 Microcosmic salt, 231 Micron, def., 519 Milk sugar, 293 Milli, def., 519 Millon's base, 145 Minium, 351 Misch metal, 455 Moissan, 160 Molal, def., 519 Molar, def., 519 Mole, def., 519
Molecular,
structure, 556
Naphthalene, 290
Natrolite, 319
Nelson
cell,
45
Neodymium,
analytical, 457
compounds, 451461
occurrence, 454
Neon,
isotopes, 506
occurrence, 13 physical properties, 14 uses, 17
Nepheline, 319
Neptunium,
chemistry, 475
isotopes, 475
volume, 519 weight, 519 Molecule, 519 Molybdates, 380 Molybdic acid, 380 Molybdenite, 370
potentials, 476 Nessler's reagent, 145 Neutralization, acids, Neutrino, 456, 489
and
bases, 171
Molybdenum,
analytical, 384 blue, 380
Neutron, 11,484,486 reactions, 495 Nichrome, 371

Nickel,
alloys,
compounds, 378
isotopes, 508
423
metallurgy, 371 occurrence, 370 orange, 353 oxidation potentials, 382, 385
steel,
analytical, 431 arsenide structure, carbide, 424

catalytic, 423 coins, 423
546
dioxide, 431
isotopes, 507
371
Molybdenyl, 379
Moment,
of force, 519 of inertia, 519
metallurgy, 421 occurrence, 420 oxidation potentials, 429, 450 physical properties, 422
plating, 423 reactions, 424
Momentum,
def., 519 Monazite sand, 333, 454
Mond
process, 421
Nickelous compounds, 429
Monel, 423 Monoclinic crystals, 545 Monosaccharides, 293 Monotropic, def., 519 Monox, 314
Niobium,
analytical, 367
halogen compounds, 365 hydride, 365 isotopes, 508
INDEX
properties, 359 reactions, 360 Nitrates,
615
Nitron, 216 Nitrosoamines, 209 Nitroso-beta-naphtol test for cobalt,
432
Nitrososulfonic acid, 195 Nitrosyl chloride, 214
Nitrosylsulfuric acid, 256 Nitrous,
acid,
properties, 215
test,
216
Nitric, acid,
hydrates, 210
equilibrium in water, 207 preparation, 207

properties, 208
manufacture, 210
oxidation potentials, 213
properties, 210
oxidation potentials, 209, 213

structure, 203 anhydride, structure, 203
reduction products, 208 structure, 203 anhydride, structure, 203

oxide,
oxide,
preparation, 203 structure, 203

Nitroxyl, 204
complex ions
of,
205, 206
preparation, 205
structure, 203
synthesis, 211 Nitrides, 194
Normal
halogen compounds, 201

Nitrites, 208
solution, def., 520 Nucleon, 520 Nucleus, atomic, structure, 484 def., 520 Nuclide, 520 Nylon, 301
Nitrobenzene, 214 Nitrocellulose, 299

Nitrogen,
analytical, 216
Obsidian, 320 Octet, def., 520 Odd molecules, 178
compounds with hydrogen, 189

dioxide,
Ohm, 520
-centimeter, 520 Oil-water gas, 282
Olefine series, 290
equilibrium in water, 207

properties, 206 structure, 203
isotopes, 506
Oleum, 254
Olivine, 306, 319
occurrence, 186 pentoxide, 210 physical properties, 188

potentials, 242
Orangite, 333
Orbital, 3
preparation, 187
reactions, 188 resemblance to carbon monoxide,
278
sesquioxide, preparation, 206 tetroxide, structure, 203 tetrasulnde, 202
trichloride, 201
triiodide,
Orford process, 421 Organic chemistry, 270 Orpiment, 218 Orthochromatic, plates, 120 Orthoclase, 319, 401 Orthorhombic crystals, 545 Osmiridium, 434
Osmium,
analytical, 448
202
trioxy fluoride, 202 Nitroglycerine, 214, 299
compounds, 440 isotopes, 510 occurrence, 434

oxidation potentials, 440, 450
properties. 435 reactions, 437
Nitrohydroxglamic, acid, 202 Nitrometer, 216
616
Osmyl compounds, 441
Overvoltage, 520, 526 Oxidation, 520 -reduction potentials, table, 528 state, 520 Oxides, 25 Oxone, 44
INDEX
Pentlandite, 420
Perch lorates, 179 free radical, 180

Perchloric,
acid, 179
structure, 157
Oxyacetylene torch, 24, 291 hydrogen torch, 25
Oxygen,
analytical, 27 chemical properties, 21
isotopes, 506 liquefaction, 23
anhydride, 180 Perferrate, 417 Perhydroxyl, 34 Peridotite, 321 Periodates, 182

Periodic, acid, 182
anhydride, 182
table, inside back cover Permanganate, analytical, 398 compounds, 395 Permanganic acid, 395 Permutite process, 75 Perowskit structure, 546 Peroxide structure, 22, 30 Peroxyacids, 32
occurrence, 19 oxidation potentials, 34, 35 physical properties, 20 preparation, 23 uses, 23
Ozone,
oxidation potential, 34 preparation, 33 properties, 33
uses,
34
Palau, 436 Palladium, absorption of hydrogen, 444 analytical, 448 compounds, 444 isotopes, 508
borate, 85 carbonate, 287 chroma tes, 378

disulfuric acid, structure, 261 molybdic acid, 381
monosulfuric acid, structure, 261 nitrogen, 215 niobates, 365 phosphoric acid, 232 stannic acid, 349
sulfuric acid, preparation, tantalates, 366
264
Panchromatic
Paper, 301
plates, 120
titanic acids, 337,
340
Paracyanogen, 295 Paraffin, 290 Paramagnetic, 520 Paris green, 112, 226 Particles, fundamental, 486
Parting, 127 Passive, 520
Passivity, of chromium, 374 of iron, 410 of platinum metals,
tungstates, 384 uranate, 384
vanadates, 363
Perplatinates, 448
Perrhenate, 396 Pervanadyl, ion, 360 salts, 363
437
406 Penicillin, 308 Penninite, 319

Pearlite,
Petroleum, 304 Pewter, 345 Pharaoh's serpents, 147 Phase, 520 Phase rule, 520 Phenol, 302 Phenolphthalein, 308, 565
INDEX
Phlogopite, 319 Phonolite, 321 Phosgene, 161
617
metallurgy, 431 occurrence, 434 oxidation potentials, 446, 450
Phosphates, 232
buffer solutions, 564
washing powders, 75 Phosphides, 231, 240 Phosphine, 224
Phosphomolybdates, 380 Phosphonium compounds, 226

Phosphorescence, 520 Phosphoric acids, 230 Phosphorous acid, 230 Phosphorus, acids, structure, 230
analytical, 241
Plumbates, 352 Plumbites, 351 Plutonium, chemistry, 477 isotopes, 476 potentials, 478 production, 500
Polarization, 101, 521 Pollucite, 42
Polonium, 269
isotopes, 511
238 hydrogen compounds, 224 in matches, 221 isotopes, 506 modifications, 218 occurrence, 217 pentoxide, 227
halides,
Polymorphism, 521
Polysulfides, 263
Porcelain, 325
Portland cement, 327 Positron, 486 Potassium, alloys, 43

analytical, 55
potentials, 242 preparation, 220 reactions of, 223
atomic structure, 37
bi-iodate, 182
sesquioxide, 227
sulfides, 239 Phosphotungstates, 383 Photoelectric effect. 221 Photography, 119
bromide, 52 carbonate, 46 carbonyl, 278 chemical properties, 38, 42 chlorate, 179

chloride, 51
color, 121
Photometer, 248 Photon, reactions, 495 Picric acid, trinitro, 297 Pig iron, 404 Pink salt, 349 Pitchblende, 357, 471 Plagioclase, 319 Planck's constant, 2, 521 Plaskon, 303
Plaster, 72 of Paris, 72
Plastics,
chloropalladate, 446
chromate, 377
cobalti nitrite, 55, 427 cyanide, 52
dichromate, 377
ferricyanide, 416 ferrocyanide, 415 fluorotitanate, 338
302
hydride, 43 hydroxide, 44 iodate, 182 iodide, 52

ion,
Platenite, 423
hydra tion, 37
444
Platiniammino-salts, 448 Platino-coordination compounds, 447
ionization potentials, 37
iridate,
Platinum,
analytical, 448 black, 435
isotopes, 506
molecule, 38
nitrate, 215
compounds, 446
isotopes, 510
occurrence, 41
osmate, 441
618
osmiamate, 441
oxidation potential, 37
INDEX
Pyrophosphoric acid, 232
Pyrosulfuric acid, 259 Pyrosulfuryl chloride, 266 Pyroxene (group), 319 Pyroxylin, 302 Pyrrhotite, 401
44 permanganate, 395
oxides,

radioactivity,
490
Qualitative analysis, 548 Quantim number, 2, 521 Quartz, 315
ruthenate, 431
ruthenocyanide, 438 silicate, 318 spectra, 38 sulfate, 53 use, 42 Potential, 521 change with concentration, 534 diagrams, 535
Pottery, 324 Powder, smokeless, 299 Power, 521
Radioactinium, 467
Radioactive, constant, 490
series,
488
Radioactivity, 485, 521
Radiothorium, 467
Radium, amalgam, 62
emanation, 511
halides, 71
Power piles, 502 Praseodymium,

analytical, 457
isotopes, 511
compounds, 451461
occurrence, 454 physical properties, 453 Prehnite, 320 Pressure, 521 conversion factors, 570 Producer gas, 221
properties of metal, 58 radioactive properties, 511

sulfate, 74 A, 488, 511 B, 488 C, 488, 511 C, 488 C", 488 D, 511 E, 511
Promethium, properties, 453 Prosiloxan, 314 Proteins, 298

Protactinium, occurrence, 469
isotopes,
F, 488
G, 488 Radon, 511

470
Proton, 1, 484, 486 Prussian blue, 416

Prussiate,
red,
Rare
earths, analytical, 459
416
yellow, 416 Prussic acid, 296
compounds, 455 ionic radii, 464

isotopes, 509 position in periodic table, 451
Pucherite, 357
Pumice, 320 Purple of Cassius, 124 Pyrene, 294 Pyrex glass, 326 Pyrites, 243 Pyrochlor, 358
Pyrogallol, oxygen test, 27 Pyrolusite, 386
preparation, 454
properties, 453
Rayon, 301
RDX
299, 300
Reaction, half, 157 Reactor,
homogeneous, 502
nuclear, 501
Pyrope, 320 Pyrophoric metal, 455
power, 502 Realgar, 218
INDEX
Rectifier,
aluminum, 93 tantalum, 359

Reduction, def., 521 Refractive index, def., 521 Replacement series, 521
Resins, amberlite, 457 ion-exchange, 460
chemical properties, 38, 42 hydroxide, 44 isotopes, 507 occurrence, 41

oxides,
44

radioactivity,
spectra, 38
490
phenol-formaldehyde, 303 thermosetting, 302

Resistance, def., 521
of metals,
Ruby, 90
Rusting of iron, 410 Ruthenates, 439 Ruthenites, 439
566
Ruthenium,
analytical, 448
Rhenium,
analytical, 396 atomic properties,
compounds, 437
388
isotopes, 508
compounds, 395
isotopes, 510

tetroxide, 439 Rutherford, 492 Rutile, 332, 336

radioactivity,
490
Rhodites, 442
Rhodium,
analytical, 448 compounds, 442
isotopes, 508
type of crystal lattice, 546 Rydberg's constant, 521

Sal ammoniac, 196 Samarium,
analytical, 457

79 Rhodochrosite, 386
test,
Rhodizonate
Rhobohedral crystals, 545 Rhyolite, 320

Rocks,
families,
320
compounds, 451-461 occurrence, 454 physical properties, 453 radioactivity, 457, 490 Sand, 314 Sapphire, 90 Scandium,
analytical, 457
igneous, 318
comppsition, 321
compounds, 451-461
isotopes, 506
metamorphic, 322 sedimentary, 322 Roentgen, unit, 504 Roscoelite, 357 Rosemetal, 345 Rouge, 414 Rubber, natural, 303 synthetic, 304 vulcanization, 303 Rubidium,
analytical, 55
occurrence, 454
properties, 453 Scapolite, 320 Scheele, 160 Scheele's green, 235
Sea water, composition, 41 Sedimentary rocks, 318 Selenates, 260 Selenic acid, 260
Selenides, 251
Selenites,
253
carbonate, 49
Selenium,
620
analytical, 267
INDEX
carbonate, 117
sulfur,
compounds with
dioxide, 253
266
complex
ions,
115
halogen compounds, 266 isotopes, 507 metallic, 247 modifications, 247 occurrence, 243 oxides, 251 potentials, 269 properties, 247
Seleno,
-acids, 265 sulfuric acid,
cyanide, 117 dichromate, 118 ferricyanide, 118 glance, 113 halides, 116, 117 imide, 194
isotopes, 508
metallurgy, 113
nitrate, 118
nitride, 117
nitrite,
118
267 Selenous acid, 253 Senarmontite, 218 Serpentine, 319

Sherardizing, 133
Siderite, 401
Silica,
occurrence, 113 oxidation potentials, 116, 119, 128 oxides, 116, 118
perchlorate, 180 phosphate, 118 properties of metal, 103, 114 pyrophosphate, 232 sulfide, 118 solubility, 103
Slag, blast furnace, 404 Smaltite, 420
315
Silicates,
303-307
analysis, 329
structure, 324
Silicic acids,
Silicides,
316 311, 312
Silicochloroform, 314 Silicoethane, 313

Silico-oxalic acid,
Silicon,
Smalt, 426 Smithsonite, 131

screens, 259 Smokeless powder, 299 Soap, 74 Soapstone, 60, 323 Soda-ash, 47 Sodalite, 319 Sodium, amalgam, 43 amide, 194
Smoke
314
amorphous, 310 compounds with halogens, 313 compounds with hydrogen, 312 crystalline, 310 dioxide, modifications, 314 heat of oxidation, 316
isotopes, 506
analytical, 55
monoxide, 314 occurrence, 309 oxychloride, 314

reactions, 311
sulfide,
atomic structure, 37 azide, 201

bicarbonate, 46 bismuthate, 237 bromide, 52
329
tetrachloride, tetrafluoride,
Silicones,
Silver,
313 313
carbonate, 46 chemical properties, 38, 42

chloride, 50 type of crystal lattice, 545
Sillimanite,
328 320
acetylide, 292
chroma te, 377 compounds, production, 47

cyanide, 52, 297 dichromate, 317 ferri-nitrosopentacyanide, 417
ferrite,
alums, 119 amalgam, 114
ammonia complex,
analytical, 122
constant, 116
413
arsenate, 118
ferrocyanide, 415
INDEX
flame
621
319
56 49 hexametaphosphate, 233 hydride, 43 hydroxide, 44

test,
Spodumene,
fluoride,
42, Stalactite, 69
Stalagmite, 69
Standard,
conditions, 522
potential, 522 Stannates, 348 Stannic,
iodate, 181
iodide, 52
ion,
hydration
of,
37
ioni/ation potential, 37 isotopes, 506 molecule, 38

nitrate, 53 occurrence, 41
348 349 sulfate, 350 sulfide, 349 Stannites, 349

acid,
halides,
oxalate, analytical, 397
Stannous,
halides,
oxidation potential, 37
oxides, 44
349
hydroxide, 348
oxide, 348
peroxide, source of oxygen, 24 peroxydisuifate, 264
phosphate, 232 physical properties, 37 preparation, 42
350 349 Starch, 293

sulfate,
sulfide,
Stassfurt deposits, 51, 160

Steel,
pyroantimonate, 236 silicate, 317 spectra, 38

sulfate, 53
sulfide,
acid resistant, 312
Bessemer, 408 case-hardened, 409
250
use,
43
Solar Energy, 504

Solder, 345
Solubilities, tables of,
chrome, 370 cobalt, 423 crucible, 409

577
high speed, 371, 407 manufacture, 407
nickel,
Solubility,
def.,
423
522
open-hearth, 407
properties, 405
stainless,
product, 522
Solute, 522 Solution, 522
371
Solvay process, 47
Solvent, 522 Sorbite, 407 Sorel cement, 70
Spallation, 493, 494, 522
tempering, 406 tungsten, 372
types of simple carbon, 406

Stellite, 371,
Spathic iron, 401

Specific,
gravity, 522 heat, 522
422 Stephan's constant, 522 Stibine, 224 Stibnite, 218, 239 Stilbite, 319 Stoichiometric, 522
Storage battery, Edison, 431 lead, 355 Strontia, 63
Strontianite, 60
values for volume, 522 Spectrum, 522

Sphalerite, 131
many
substances, 567
Sphene, 332 Sperrylite, 434 Spiegel iron, 387 Spinel, 60, 95
Strontium,
analytical, 77
carbonate, 69
halides, 71
622
hydroxide, 67
isotopes, 507
INDEX
Superphosphate, 231 Surface tension, 522 Syenite, 320 Symmetry, elements System, 522
Tachydrite, 70 Talc, 60, 323 Tantalates, 366 Tantalic acid, 366
metal properties, 58, 60 nitrate, 76 oxide, 63 spectra, 79

sulfate, 73
of,
544
Styrene, 304 Sucrose, 293 Sugar, 293
Sulfamic acid, 265 Sulfamide, 265 Sulfate, 259 analytical, 267 Sulfathiazole, 307
Sulfide, analytical,
Sulfites,
Tantalum,
carbide, 367
267
properties, 250
253
Sulfur, analytical, 267
dioxide, 251 flowers of, 246

halides, 266 in illuminating gas,
247
isotopes, 506
milk
of,
246
monochloride, 266 monoclinic, 245 occurrence, 243 oxides, 251

potentials, 269 properties, 244
halogen compounds, 366 isotopes, 510 metallurgy, 358 monoxide, 366 nitride, 367 occurrence, 357 oxidation potentials, 361 pentoxide, 345 properties, 359 reactions, 360 sulfide, 367 Tartar emetic, 236 Technetium, chemistry, 395 preparation, 387 Teflon, 302 Telluric acid, 260 Tellurides, 257 Tellurites, 253
Tellurium,
analytical, 265 complex iodide, 268
chloride, 255
rhombic, 245 sesquioxide, 251 trioxide, 254

Sulfuric acid,
compounds with
dioxide, 254
halides, 266 iodide, 255
sulfur,
266
as oxidizing agent, 259
commercial" uses, 258 electron structure, 254 hydrates, 258 ionization constants, 258 manufacture, 254, 255 physical properties, 257 Sulfurous acid, electron structure, 253 oxidation by nitrite, 208 oxidation potentials, 252 properties, 252
Sulfuryl,
isotopes, 508
monoxide, 254
occurrence, 243 oxides, 251
potentials, 269 properties, 248
trioxide,
260
Tellurous acid, 254 Telluryl compounds, 254 Temperature, def., 522
Terbium,
amide, 194
chloride,
266
analytical, 457 compounds, 451-461
INDEX
623
C", 488 D, 488
subgroup, 461 Tetragonal system, 545 Tetrathionic acid, 261-263 Tetryl, 300 Thallic compounds, 154
Thallium,
analytical, 154 isotopes, 510
X, 488, 511
Thoron, 511 Thulium,
analytical, 457

Tin,
alloys, 343,
metal, 149 occurrence, 148 oxidation potentials, 155
344
analytical, 355 disease, 343

foil,
Thallous compounds, 144 Thermite, 93 Thermoelectric force, 523 Thioantimonates, 239 Thioantimonites, 239 Thioarsenates, 239
Thioarsenites, 239 Thiocarbonate, 265, 289
344
hydride, 350 hydroxide, 348

isotopes, 508 metallurgy, 342 occurrence, 341 oxidation potentials, 348
oxides, 349
Thiocyanate, 298 Thiocyanic acid, 265 Thiokal, 304 Thiomolybdate, 381 Thionic acid, preparation, 263 Thionyl chloride, 266
Thiostannates, 350 Thiosulfate, complex ions, 262 reactions, 262 reaction with iodine, 183 Thiosulfuric acid, 261, 262
Thiotungstates, 384 Thiourea, 298 Thiovanadites, 364, 367 Thoria, 468 Thorianite, 467 Thorite, 467
Titanate, 337
Titanite, 319
Titanium,
analytical, 340 compounds, 335
isotopes, 506

properties, 334 sulndes, 338
Thorium,
analytical,
Titanous chloride, in determination of iron, 420 Toluene, 290 Topaz, 319 Tourmaline, 82, 319 Trachyte, 320 Transformation series, 488
Transition series,
first,
469
chemistry, 468
399
compounds, 468
emanation, 447 isotopes, 467 metal, 467 occurrence, 466 properties, 468
series,
second, 433
third, 433 Transmutation, 493 Tremolite, 319 Tribromaniline, 160
488, 489
Trichlornitride, 201 Triclinic crystals, 545
A, 488 C, 488, 511 C', 488, 511
Tridymite, 315
Triiodide, 173
Trinitrobenzene, range, 56S
624
Trinitrotoluene, 299 Triple point, 523 Trithionic acid, structure, 261 Tritium, 12
reactions,
INDEX
Vanadites, 362
Vanadium,
analytical, 367
compounds, 360
isotopes, 506
494
Tungstate, 383 Tungsten, alloys, 372 analytical, 384 blue, 383 compounds, 381 cyanide, 297 isotopes, 510 metallurgy, 371 occurrence, 370 oxidation potentials, 382, 385 reactions, 373 Tungstic acid, 384 Turnbull's blue, 417 Turquoise, 90
metallurgy, 397 occurrence, 357 oxidation potentials, 360, 368

Vanadyl, ion, 360

salts,
Van
362 der Waals' equation, 523
Venetian red, 414

Vermilion, 146 Vesuvianite, 320 Vinyl, group, 292 plastics, 302 Vinylite, 302 V-particles, 503 Viscose, 301 Viscosity, 523
Type
green, 426 metal, 345
Ultramarine, 98
Unsaturated compounds, 272 Uranates, 474

Uranite, 471
Vitamines, 306 Vitellin, 217

Vitriol blue, 111
Uranium,
chemistry, 474 ferrocyanide, 475 assion of U 235 497
,
Volborthite, 357 Volt, 523 Volume, conversion factors, 570
metallurgy, 472 occurrence, 471

potentials, 473
Washing
Water,
,
soda,* 47
separation of
series,
236
499
crystal structure, gas, 281

glass,
28
488
317
471 X, 467
II,
purification, 30 softening, 74 table of densities, 558
470 Y, 467 Uranyl compounds, 474 Urea, 197, 209, 298, 306 resins, 303 synthetic, 306
2,
table of vapor pressure, 560 Watt, def., 523 Wave-length, 523 Weight, conversion factors, 570 Werner, 428
Valence, 523
terms of electron-pair, 271 octet theory, 7, 16, 157 of carbon compounds, 271 Vanadates, 363 Vanadic acid, 362 Vanadinite, 357
in
White lead, 354 White metal, 345 Willemite, 131, 319

Witherite, 69
Wolframite, 370 Wollastonite, 320 Wood, pulp, 300
INDEX
Wood's metal, 223 Work, conversion factors, 570
Wurtzite, structure, 546
,
625
aluminate, 95
analytical, 138
Xanthrate, 301
,,jgart)onate,
blended, 131 137

ions,
Xenon,
isotopes, 509
chromate, 378
complex
134
occurrence, 13 physical properties, IS
ferrocyanide, 138, 416 galvanized, 129

halides, 136
Xenotime, 453 X-rays, 523

Ytterbium,
analytical, 547
hydroxide, 135
isotopes, 507

subgroup, 461 Yttrium, analytical, 451 compounds, 451-461 isotopes, 507 occurrence, 454 physical properties, 453 subgroup, 452 Yttrocerite, 454
Zeolites,
metallurgy, 131 occurrence, 131 oxide, 135
type of crystal lattice, 546 properties of metal, 130, 133 spelter, 132
sulfate, 136
sulfide, 131,
137
crystal lattice, 546 Zincate, 135

Zincite, 131, 135 Zircon, 319, 333
Zirconium,
analytical, 340
compounds, 338
319
isotopes, 508
process, 75
occurrence, 332
properties, 334
Zinc,

Principles of Chemistry

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THE BOOK WAS

OSMANIA UNIV1RSITY LIBRARY

PROFESSOR OF CHEMISTRY IN THE UNIVERSITY OF CALIFORNIA

ASSOCIATE PROFESSOR OF CHEMISTRY CALIFORNIA

Sixth Edition Copyright, 1952, by

The Macmillan Company

any form without permission in except by a reviewer who wishes

book may be reproduced in writing from the publisher,

PRINTED IN THE UNITED STATES OF AMERICA

PREVIOUS EDITIONS COPYRIGHT, 1918, 1926, 1932, 1940, AND 1947, BY

THE MACMILLAN COMPANY

PREFACE TO THE SIXTH EDITION

maintain the prac-

tice of thirty-four years, first, of incorporating

JOEL H. HILDEBRAND RICHARD E. POWELL

PREFACE TO THE FIFTH COITION

One who merely

in such a fluid state that it lends itself readily to this

the oldest knowledge

course, the intellectual appetites

PREFACE TO THE FIFTH EDITION

State what you can about the concentration of

(2) 0.2 7V-H 2 SO 4 (3)

and 0.02M-HC1 in the same solution.

the ionization constant of the

PREFACE TO THE FIFTH EDITION

last of these offers excellent drill, in

both qualitathe principles of equilibrium as

The students have Bronsted concept. We make the

PREFACE TO THE FIFTH EDITION

believe the Bronsted theory

ignored completely decidedly not in favor of 'going Bronsted' in the freshman

in the analytical courses that follow.

for specific contributions, to Dr.

James Arthur Campbell, now of Oberlin College, Ralph R. Hultgren, Pro3-6 in

fessor of Physical Metallurgy, for the prints for Figs.

KINDS OF MATTER WEIGHT RELATIONS IN CHEMICAL REACTIONS

306 328 353

FINAL EXAMINATION QUESTIONS

APPENDIX II. ANSWERS TO EXERCISES AT THE ENDS OF CHAPTERS

propriate at the beginning of a

find that chemistry

from the liquid or gaseous

point ^Coefficient of expansion

Conductivity for heat Conductivity for electricity

Magnetic susceptibility +Melting point

Emission spectrum Emissivity

marked by +. Use may be made of the Book of Inorganic Chemistry, p. 513,

proportions of baking soda and cream

of tartar should be used for a

methods such as are

which are appropriate

for scientific treatment.

which no mix flour,

baking powder, sugar,

the properties of a solder which

same kind together constitute

a phase, and a mixture containing more than one phase

three phases: quartz, mica, and feldspar.

heterogeneous. So is the freezing mixcream all of the pieces of ice together

aqueous medium), fog

droplets in gas), and smoke alloys appear uniform to the eye,